Captain America: Played surprisingly straight with Viper/Madame Hydra. Despite her partnership and romantic relationship with the Silver Samurai, early stories claimed that she was incapable of feeling love for anyone. More recent stories revealed that she was genuinely in love with the Samurai and still misses him. She also views her frequent foe Spider-Woman/Jessica Drew as the closest thing she has to a family, displaying some affection for her.
Bullet, a professional assassin, has an autistic son named Lance. Lance is the one thing in the world Bullet cares for and he'll do anything to protect him.
Purple Man, who has six children (all are from different mothers, all have inherited a weaker variant of his powers, and one has actually become a supervillain herself). He genuinely loves each and every one of them and has made multiple attempts to forge a bond with them. In a rather disturbing twist on this trope, finding out about his first daughter actually made him an even worse person; before he was happy to retire from supervillainy and just used his powers to live a life of comfort and hedonism. After he learned of her, he decided to come out of retirement and started pulling far bigger crimes than he ever committed before, as he believes he can win her affection and respect by doing so.
He also used to have a wife, whom he really did love. However when she learned about his powers and that he had used them to pressure her into marrying him quicker, she understandably flipped out and left him, which simply made him even more bitter and amoral. Given Purple Man's usualtendencies, it says a lot that he actually let her leave and didn't pursue or harm her.
On the other hand, he had no compunction using his powers on the five Purple Children, despite his claim that the reason he sought them out and basically kidnapped them was to be loved without using his powers (and also because with all their powers together, they could rule entire countries). Their response to this was to use their combined powers to make him walk in front of a train.
Doctor Doom's adoration of his deceased mother, Cynthia, is possibly his only unambiguously good trait. Not only that, but he simply adores Valeria Richards, and swore on the moment of her birth (which he aided in), that he would defend her with his life, and that anyone who sought to do her harm would have to deal with his wrath. In this case, Valeria cares for him as well. The girl's first word as a baby was "Doom."
To a lesser extent, Depending on the Writer, Doom feels the same way about the people of Latveria. Threaten them, you will suffer Doom's wrath.
The Puppet Master is a vile and evil man, but his one good trait is that he genuinely loves his stepdaughter Alicia. He initially planned to crash Alicia's wedding to Johnny Storm by killing the groom, but couldn't go through with it after seeing how happy she wasnote Though this "Alicia" would later turn out to be a Skrull impostor..
When Ben Grimm and Alicia finally got married in the 2010s, Puppet Master took radioactive clay and sent the Immortal Hulk after the Thing. The only thing that deterred him from his control of the most evil and scary version of the Hulk was when Alicia was endangered. Unfortunately, this meant that the most evil and scary version of the Hulk was still uninhibited and felt like fighting the Thing anyway..
The Hood: The Hood is a textbook example of this trope, using some of the proceeds from his criminal activities to pay for his mother's care while also supporting his pregnant girlfriend Sara. The main villain the Hood "fights" during his first mini also counts; he loves his family greatly and was trying to find a mutant to be part of his supervillain squad because his daughter was one and asked him to hire some more.
The Incredible Hulk: Despite General Thaddeus "Thunderbolt" Ross/Red Hulk being a type IIIAnti-Villain, it is clear that he loves his daughter Betty. From what we've seen in flashbacks, he loved Betty's mother Karen too; her death from cancer left him emotionally devastated.
The Mighty Thor: The Absorbing Man and Titania are both mean, violent thugs, but are married and genuinely love one another. Averted in terms of Absorbing Man's ex, who is Stonewall's mother. Stonewall is the result of Creel raping Jerry's mother, and Creel doesn't care for Stonewall either.
Before his transformation into Thorn, dialogue hints that mobster Sal Carbone gets along well with his niece Rosalie. He's also upset when his Red Shirt nephew Marco (the son of an otherwise unmentioned third Carbone sibling) is killed while his brother Julius cares more about how Marco and his companions accomplished their objective before dying.
The vile Human Traffickers Cristu Bulat and Vera Konstantin from "The Slavers" arc are in a romantic relationship and are sincerely in love. When interrogated by the Punisher, Cristu refuses to tell him anything about Vera until he starts gutting Cristu.
Similarly, snuff filmer Mickey Fane from the "Naked Kill" one-shot loves his girlfriend/accomplice Polly Hu and regrets letting her get killed by the Punisher, with his final scene showing him holding a private mourning session for her before the Punisher arrives.
Leon Rastovich, the ringleader of a child pornography ring, was offered a lighter sentence if he sold out his partners. He agreed and sold most of his partners up the river, but no matter how much reduction in jail time they offered him, he refused to sell out his mother (who was responsible for providing him with victims). Once he's paroled, the first thing he does is drop by her place for dinner.
The MAX version of the Kingpin is so utterly selfish that he even allowed one of his rivals to cut his son's throat in front of him rather than give him any ground. But when his wife betrays him he can't bring himself to execute her and simply kicks her out of his house.
The violently unhinged mobster Theresa Gazzera cared deeply for her brother Carmine/"Pittsy" before he was killed by the Punisher, graphically threatening anyone who speaks ill of him and flying into a mindless frenzy when she runs into the man who killed him. She also has a crush on her boss Nicky Cavella and serves him with an almost religious fervour, having a complete breakdown when he spurns her.
The Mennonite, an enigmatic mob hitman hired by Kingpin to take down the Punisher, is one of the only villains in the MAX series to elicit even a modicum of sympathy due to this, as he agrees to go after the Punisher as One Last Job in return for the money to pay for his ill wife's treatment.
Downplayed in the case of ruthless IRA terrorist Finn Cooley and his nephew; though Finn leaves him to die, he wasn't happy about it and gets angry at his fellow terrorist Michael for not appreciating the sacrifice he made in doing so. The same arc also plays it straight with Napper French, a Retired Monster known for dismembering his victims alive, who is blackmailed into coming out of retirement by threatening his beloved grandson, and crime lord Brenda Toner, who cares about her kids enough to try and prevent them from seeing her husband after she has him killed so as to avoid traumatizing them.
The Kingpin is a ruthless Manipulative Bastard mob boss who rules the New York underworld with an iron fist. However he deeply loves his wife and son, even after both tried to murder him. They both died, which has done nothing but make him more cold and bitter. He later fell in love with a woman named Marta and tried to leave the business to be with her. When Lady Bullseye and the Hand killed Marta, Fisk came back to New York with a vengeance.
It's also subverted: Kingpin's beloved niece, Samantha, is kidnapped by a rival gangster named Fade that is attempting to muscle in on Fisk's territory. Fade intends to use the poor girl as leverage against her uncle, and an enraged Fisk pays a healthy ransom to ensure her safe return. Fade also agrees to give Samantha a letter from her mother to help comfort her before her release. Unfortunately for Fade, the letter was doctored with the trigger scent, and "Samantha" is actually X-23...
Kingpin also has a real best friend, Miles Morales (no, not that one), who saved his life in prison. When he wanted to drop the gangster life, Kingpin helped to Unperson him, and when his wife died, he gave him the means to reunite with her alternate version in the Ultimate Marvel universe.
The Sandman apparently had a mother he loved too much to let her know he lived a life of crime, so he changed his name to Flint Marko. When he was bitten and seemingly killed by Venom, he asked Spider-Man to tell his mother he was sorry for not being a good guy. He also has a daughter named Keemia (or at least he believes himself to be her father) whom he is deeply protective of (although he may have killed her mother and then blotted out the memory). She was later taken away from him by Child Protective Services due to his kidnapping her. Since Spider-Man was involved, this has made the feud between the two more personal and bitter than it ever was before.
Norman Osborn genuinely loved his deceased wife. Whether he loves his son or not depends on the writer.
Tombstone is pretty ruthless in the business but, as shown in The Superior Foes of Spider-Man, he still deeply loves and cares about his daughter. In a rare instance of the loved ones also being villainous, said daughter is Janice Lincoln, the supervillain known as Beetle; she also is shown to love her father. In another twist on this trope, Janice was well-aware of her father's lifestyle and business (in fact it was partly what inspired her to become a supervillain, much to Tombstone's consternation) but still had a fairly normal childhood.
In The Amazing Spider-Man (J. Michael Straczynski) #503, Spider-Man discovers that Loki has a mortal daughter named Tess Black (among hundreds of others). Tess gets possessed by a powerful agent known as Morwen - who is a threat to Loki's power. If he didn't care about Tess, he would have killed her in order to stop Morwen. But apparently, he does not neglect his children, and at first demands Tess's release. When that fails, he asks for Spider-Man's help to save her, they go through a difficult process in order to get Tess back alive which causes more problems, and at the end of it Loki admits that he owes Spider-Man a debt for helping him save her. Yep, the God of Mischief and resident Magnificent Bastard is a Papa Wolf. Who knew?
Loki makes a point of not having loved ones close who would provide easy targets for his many enemies (he wipes Tess' memory for one), so to what extent he would go to save them is rarely shown... then his innocent and good-ish child version told his only friend (possibly more) that he would rather see the nine worlds burn than to lose her again. And he meant it too - he actually postponed the world-saving to save her.
In another example from Spider-Man's rogues gallery, Adrian Toomes, the Vulture, has a little grandson whom he adores. When the kid developed a brain tumor, Toomes went on a crime spree to try and make enough money to pay for treatment, but was thwarted by Spider-Man. He was so enraged that he put Spidey in the hospital over it. It was later revealed that he also has a granddaughter named Tiana, and that he used to leave her and her mother some of the money from his heists to help make up for his son having abandoned them.
Zig-zagged with Thanos and his adoptive daughter Gamora. He treats her far, far better than his other children but he still has no qualms about putting her through Training from Hell and almost killed her when she betrayed him for Adam Warlock. Regardless, Thanos’s few Pet the Dog and Papa Wolf moments are concerning Gamora, meaning she’s likely one of the few things he cares about (after Death of course).
Speaking of Thanos, his Elite Mooks Corvus Glaive and Proxima Midnight are the married members of the Black Order who have been shown to be in a genuinely loving and affectionate relationship despite being sadistic genocidal monsters to everyone else. They prefer fighting as a Battle Couple and coordinate their attacks while referring to each other by pet names such as 'my love' and 'dear midnight'; something that they continue to do in the Avengers: No Surrender event. Proxima has displayed great despair or anger whenever Corvus has fallen in battle (even though she knows that her husband is effectively immortal and will regenerate given some time); while Corvus has shown to admire and indulge his wife's Blood Knight tendencies with gifts of 'first blood' whenever she wants.
Magneto (though "evil" may be stretching it with him) famously has his three children Quicksilver, Scarlet Witch and Polaris, all of whom he deeply loves even when they're aiding The Avengers and X-Men against his schemes. His also genuinely loved his deceased wife and became a villain expressly because of losing his family in the Holocaust (in fact being separated from his mother is what caused his powers to activate). When he is forced kill Scarlet Witch during the attack on the Avengers in Old Man Hawkeye, he genuinely cries.
His Ultimate X Men incarnation, who's far more despicable, also qualifies, though it's very downplayed. Emphasis on downplayed because he does love and favor Wanda, though his favoritism toward his daughter is treated as a bad thing, plus he unleashes Ultimatum in response to her possible death.
Sabretoothloved his mother, one of his enemies even referring to him as a mama's boy given the extent of Creed's doting on her in the nursing home when he visits. The only others Creed really bonded to were love interests, Mystique, Holly, and Bonnie. He thought about settling down with Holly, and going away with Bonnie. Sadly both died not long after they got together. He & Mystique were off-and-on since 2010, and were shown to be very affectionate when they were together.
Weapon X (2017) reveals that Creed genuinely loves his normal human son Graydon (whom he had with Mystique) and despite Graydon despising him, Sabretooth saves his son from Hell after his mother Mystique killed him.
Speaking of Mystique, the one person she loves more than anyone is definitely her wife Destiny, who's the one person Mystique has never once betrayed. When Destiny died, Mystique went on a Roaring Rampage of Revenge, and went on to care for her biological son Nightcrawler and adoptive daughter Rogue greatly, even performing a Heroic Sacrifice once for them. But with even with all that said, she has no qualms about hurting and betraying them.
Though not necessarily evil, Emma Frost is usually depicted as one of the more cold, pragmatic and morally gray members of the X-Men. Despite this:
She cares deeply for her daughters/clones the Stepford Cuckoos, and vows revenge on Jean Grey and the Phoenix for killing the other thousands of them in Phoenix: Warsong.
She's also cares for her students, and even killed her own sister after said sister's actions resulted in the death of Synch in Generation X. When a bunch of the students were killed by William Stryker's forces after House of M, she was devastated.
Ultimate Spider-Man: This aspect of Kingpin's character is a plot point; it's revealed that Wilson's wife fell into a mysterious coma before the start of the story. Kingpin uses his resources to care for her and strictly refuses to allow any discussion of criminal activity in front of her ("She's an ill woman. She doesn't need her head filled with our ugliness."). After a particularly difficult storyline, Daredevil decides that the only thing a man like him would understand is the murder of his wife, and Spider-Man has to try and convince him that enacting this plan would make them as bad as each other.
Ultimate X Men: Blob pleaded with Magneto at one point to bring his daughter Firestar and her mother to the Savage Lands to protect them from danger, despite them wanting nothing to do with him. He even had an life insurance policy in place to take care of Firestar and her mother after he died on the condition they also take care of his illegitimate son from another relationship.
