The psychological crime series Hannibal is overflowing with serial killers, but the giggling, gleeful Mason Verger stands out as particularly nasty. With little to no motive, he physically and probably sexually tortures his own sister and God knows how many others and mixes their tears into martinis. He also raises pigs to eat human flesh because, hey, why not? Not to mention when he kidnaps and paralyzes his sister in order to give her a surprise abortion.
The Reavers from Firefly. If given half a chance, they'll rape you to death, eat your flesh, and sew your skin into their clothing. And if you're very, very lucky, they'll do it ...In That Order. What's especially ironic about them is that they were created by a group of Lawful Stupid scientists in a botched attempt to find a drug that would render mankind completely good, peaceful and law-abiding.
Arlo Givens from Justified is an impulsively violent, abusive, selfish man. It's established throughout the series that some of his flaws are brought on by bipolar disorder and possibly even some form of dementia or schizophrenia. However, even when lucid and medicated, Arlo will do just about anything to save himself, up to and including stealing from his wife and attempting to betray his son to a murderous drug cartel. He has no respect for family, tradition, or any institution other than his own person. Even when given the chance to help himself by being an informant for the Marshals' Service, he's unable to commit to any form of orderly or responsible behavior.
Raylan: You know tornado weather? Sky turns green, and you know something's coming. Some days, that's the way it was in the house. Arlo would ask a question, you tried desperately to come up with the right answer, what he wanted to hear, except there wasn't any right answer at all. It was going south no matter what you said or did.
The coldly stoic Marlo Stanfield of The Wire demonstrates how Chaotic Evil doesn't necessarily mean stark-raving mad evil. He is simply Chaotic because there isn't a single thing about human life that matters to him, and is driven less by a desire for profit and more by his desire to prove his name. There isn't a single thing he won't do, no line he won't cross, to achieve what he wants.
The Shadows from Babylon 5 are perceived like this in the beginning — an ancient, sinister race that emerges from the deepest bowels of the cosmos to annihilate everything in its path with world-shattering firepower and insidious treachery. The truth turns out to be a bit more complicated. Essentially, they are everything mentioned above, except that their ultimate goal is to kick-drive their enemies (whom they actually see as students) up the evolutionary and technological ladder. Thus, they are perfectly happy when they eventually lose the battle and are driven away to return in a thousand years for another "lesson".
Anubis of Stargate SG-1. The Goa'uld themselves are already as evil as (if not worse than) Adolf Hitler. Anubis was banished by the Goa'uld because he was too evil even for them. Ultimately, his goal was to erase all life in the galaxy and replace it with new creations that would worship him as a god.
Davros of Doctor Who, Mad Scientist creator of the Always Chaotic Evil Daleks. Anything that isn't Dalek is on his "to kill" list, including his own species. He's completely batshit insane and immune to any kind of reason or attempts at negotiation.
An argument could be made that his creations, the Daleks are Lawful Evil members of a Chaotic Evil race. Consider that an individual Dalek obeys authority unquestioningly, submits to strict rules of behaviour and never ever thinks for itself, while the Dalek Emperor and its underlings, the Dalek Supremes, enforce those rules and orders and expect to never be questioned. But the entire race when viewed as a whole has only one desire: destroy everything that is not Dalek. This is the textbook definition of an Always Chaotic Evil race.
The resurrected Master is basically undead, eata people, and alternatively wants to blast the Doctor with energy bolts or ignores him. His behavior is erratic, and he works with people and then betrays them. That, and he's batshit insane. To be fair, Rassilon can be blamed for a lot, if not all, of that. He implanted in the Master's head the drumbeat that caused him to go insane as part of his Batman Gambit to end the Time War, making him indirectly responsible for all the Master's villainous actions throughout the history of the show. The Master's Heroic Sacrifice towards the end of The End of Time suggests that Chaotic Evil is not really his true nature, but simply a consequence of what was done to him.
The Black Guardian is an Anthropomorphic Personification of Chaos and is pretty evil, wanting to throw the Universe into eternal chaos.
Despite trying to seem Chaotic Good, it could be argued the Tenth Doctor veers toward Chaotic Evil. As this image argues "Who else could drown your children and put you into an eternal prison?" In The Waters of Mars he certainly seems to slip towards this, deciding that as the Last of the Time Lords he has command over the Laws of Time. There is even an argument that the Tenth Doctor's death was partially due to him thinking he was slipping too far into this territory. If it wasn't for him regenerating into Eleven, then who knows how far-gone he could have become?
Angelus, a vampiric Serial Killer who liked to watch his victims crumble — for years in Drusilla's case — before finishing them off.
Glory tells one of her minions that her power lies not in mercy, but in torture, death, and chaos. She's a vapid and shallow bully who just happens to be able to break buildings down with her fists and drink people's sanity through their skulls, and mostly just wants to have fun like just an immortal, insane hellgod can.
Warren Mears. Unlike most of the show's villains, he's not a demon, vampire, or other kind of supernatural creature, just a regular (though impossibly intelligent) guy who got bored one day and decided he wanted to be a Super Villain. His lackeys Jonathan and Andrew believe in maintaining a certain standard of ethics in super-villainy, which prevents them from actively trying to kill Buffy, but Warren feels this goes against the whole point of being evil in the first place.
In general, Vampires and demons (well, the genuinely malevolent ones for the latter, since as the franchise goes on, more heroic and/or sympathetic demon characters are introduced) tend to be of this alignment. While a few, like The Master, Mayor Wilkins, and Halfrek, seem to have some kind of bizarre, twisted code of honor, generally the only rule with these supernatural monsters is that there are no rules. Justified with vampires since each is basically The Heartless mixed in with a Revenant Zombie - Namely, a human corpse who has the original person's soul replaced with an extradimensional and hostile demonic spirit, and the demonic spirit in question then builds a personality for itself based after the (usually negative) memories of the original person in life.
Kamen Rider 555: Kitazaki/the Dragon Orphnoch, who himself takes a few cues from Asakura up there. He's only loosely aligned with the rest of Lucky Clover and cares for little other than entertaining himself through "games" that always seem to involve fighting and killing. Case in point, in the final episodes he tries to slay the Arch Orphnoch, whose existence is needed for the continued survival of the Orphnoch race, simply to prove himself the strongest.
Kamen Rider Drive has Dr. Tenjuro Banno, a narcissistic psychopath who seeks to prove his genius by forcibly digitizing everyone and making them bow down to him. Considering how petty and sadistic he is, one shudders to think what a world where he is an absolute god would be like.
Isaac desires to Restart the World and create a new one where humans are perpetually tormented, simply because he's bored of being immortal and wants to find a new way to amuse himself. Late into the series, he attempts to kickstart a world war between the countries of the world, promising only the victor will be spared, and when violence doesn't break out, he opts to do the job himself and begin wantonly razing cities.
Storious is a subtler case of this, but he still betrays each of his allies and his end goal was to destroy everything out of a nihilistic desire to be the one to write the world's "ending."
The League of Gentlemen: Papa Lazarou and the Pandemonium Circus. The open road, a life in showbusiness, no rules, no laws — like that one about not kidnapping people.
War, Famine and Pestilence, three of the Four Horsemen of the Apocalypse. Death, on the other hand, was more True Neutral than Chaotic Evil. He had a job to do, and the whole 'End of Days' thing was getting in the way.
Abaddon in season 9 is noted several times to be a brute who prefers violence, deal-breaking, and a much more chaotic hell than Lawful Evil Crowley.
Dick Roman, and Leviathans in general, are Eldritch Abominations who hate everything other than themselves and seek to kill all other forms of life.
Lucifer, though he was originally some kind of Lawful, has definitely become this by his first appearance. His main goal is to Kill All Humans out of jealousy that God loves them more than him, but he's also an Absolute Xenophobe, plotting the extinction of pagan gods for no apparent reason, and even wanting to eliminate his own minions, the demons.
Lucifer: No one gives us the right, we takeit.
Larry, the Psycho for HireEvil Mentor on Burn Notice. No morals, no conscience, and no loyalty to anyone except Michael, and only because he remains absolutely convinced that they're really not that different. And possessed of both sufficient impulsiveness and deviousness to always keep you guessing whether he's pulling an Indy Ploy or just good at the old Xanatos Speed Chess.
Joey Heric on The Practice. In his first few appearances, he repeatedly commits brutal murders just to see if he can get away with it. When it becomes obvious that he can, he starts framing innocent people for his murders to see if he can get away with that, too.
Jim Moriarty of Sherlock is a giggling, mood-swingingPsychopathic Manchild who also happens to be one of the most intelligent and manipulative criminal masterminds in the world, for no other reason beyond his constant need to fend off boredom. He's so dedicated to tormenting Sherlock that at the end of series two, he gleefully shoots himself in the head, just to prevent Sherlock from beating him at his own game.
Merle from The Walking Dead fits this quite well, with emphasis on Chaotic. The guy roams around as a free agent, doesn't care about anyone except him and his brother, and doesn't hesitate in pulling the worst shit for a second.
Gyp Rosetti from Boardwalk Empire. Five minutes after we meet him, he beats a well-meaning passerby to death with a tire iron over a perceived slight, then steals the dead man's dog for the hell of it.
Jerome Valeska from ''Gotham is an Ax-Crazy, laughably evilmonster clown, and the Joker in all but name for a few seasons of the Batman prequel show. His identical twin brother, Jeremiah Valeska, who is the only one of the brothers to survive long enough to become the Joker, actually starts out as more of a neutral evil chessmaster for most of his appearances, until he undergoes one last painful chemical transformation that causes serious sanity slippage and fully transforms him into the Joker.
Peter Pan was a strict Type 4, while his past self, Malcom, was a Type 1. As Malcom, he was a sleazy Con Man who would try to scam people out of their money and was neglectful toward his son, and then he abandoned him. Though he was a heartless Jerkass, he wasn't really a terrible threat. After de-aging and becoming Peter Pan thanks to the magic of Neverland, he's become far more calculating and patient, willing to formulate plans that would take centuries to come into fruition. However, his plan only boils down to "Take Henry's heart, become a Physical God, rule Neverland forever". When the heroes and Regina and Rumple foil his plans, his new plan is to cast a new curse where they all suffer forever because they foiled his plan.
Zelena/The Wicked Witch of the West bounced between a Type 1 and Type 2 example. In her introduction, her motive is simply to get revenge on Regina because she got to live the life that Zelena couldn't. Aside from this, she had no clearly defined goal, though she was willing to harm anyone if she thought it would help in her revenge scheme. This is due in part to her wildly aggressive emotions, which was why Rumplestiltskin didn't choose her to cast the curse.
The Sopranos: Christopher Moltisante, 110%. He's an ax-crazy sociopath who is ruled entirely by impulse and has zero empathy for anybody. Not even his girlfriend.
Chikyuu Sentai Fiveman: Galactic Super Beast Vulgyre, the true ruler of the Galactic Imperial Army Zone. It's a selfish, cruel Eldritch Abomination driven by a desire to become immortal through a ritual that involves wiping out all life on 1000 planets, all so it can become a god with free reign over the Milky Way.
The Jakanja in Ninpuu Sentai Hurricaneger become this once we learn what their true goals are that being to invoke an ancient evil power and use it to destroy the universe and remake it In Their Own Image.
The Deboth Army in Zyuden Sentai Kyoryuger seeks to destroy all life on Earth before moving on to other planets. Being centered around a cosmic horror dubbed the "planetary illness" will do that to you.
Callisto from Xena: Warrior Princess is a classic example, having witnessed Xena kill her family when she was young. She grew up with a desire to get revenge on Xena, learning how Xena fights to the point that she's capable of going toe-to-toe with the warrior princess herself. However, her quest for vengeance and her own grief drove her insane to a point that she's willing to slaughter anyone that stands between her and her goal. When she discovers that Xena has undergone a Heel–Face Turn, she begins murdering innocent people in Xena's name both to ensure people still hate Xena and to lure Xena to her so she can kill her. She fails, and doing so breaks her so completely that she ends up becoming one of the most chaotically evil recurring villains in the show.
Neutral Evil or Lawful Evil, the violent, unpredictable, and Ax-Crazy Tuco Salamanca is definitely this alignment.
image argues "Who else could drown your children and put you into an eternal prison?" In The Waters of Mars he certainly seems to slip towards this, deciding that as the Last of the Time Lords he has command over the Laws of Time. There is even an argument that the Tenth Doctor's death was partially due to him thinking he was slipping too far into this territory. If it wasn't for him regenerating into Eleven, then who knows how far-gone he could have become?