Opening up at Montana's Big Sky Billards Room, Spider-Man is face-to-face with a walking fire hazard... the Molten Man. His skin covered in a superheated metallic alloy, this intense new adversary is setting everything he touches ablaze, and Spidey can't lay a punch on him because of the heat. As Spidey gets thrown across the burning room, he spots Mary Jane and Liz Allan hiding behind a counter (as if he didn't have enough to worry about already).
The scene flashs back to earlier that day, where Peter is waiting to meet Liz by the fountain and apologize for his lackluster performance as her boyfriend. Liz has her own problems, as her brother Mark has not been seen for days and she is worried that he's gotten into trouble again. She explains that Mark is a habitual gambler, but is frequently in debt to his bookkeeper Blackie Gaxton and often ends up getting into more trouble when he resorts to crime in order to repay his loans. Harry chimes in and explains that Mark can only help stop his addiction when he's ready, but Peter decides to turn to Spider-Man as a first step.
At the Big Sky, Mark is indeed in deep with Blackie, but is confident that he'll win it all back on his next horse race. Suddenly, the Green Goblin flies in to announce his new ownership as the Big Man, and he approaches Blackie with a favor. Blackie is eager to oblige, as he's got the perfect sap for the job.
Blackie takes Mark to an abandoned police station, which has been converted into a laboratory run by Norman Osborn and Dr. Miles Warren. Having studied the subdermal process that created Sandman, Dr. Warren claims to have perfected it through nanotechnology, and Blackie has offered that Mark be the test-subject in exchange for striking his debts. The process succeeds and leaves Mark with an indestructable subdermal coating on his skin, which he can mentally switch on and off at will.
With his new powers, no debt, and a complimentary $100 from Blackie, Mark heads to the racetrack in hopes of continuing his hot streak, unaware that Spider-Man is watching from afar. When his horse comes in last, Mark is so distraught that his armor activates against his will, then superheats itself until he's setting fire to the track. Spidey is forced to intervene, but the "Molten Man" overpowers him easily and escapes.
Meanwhile, Mary Jane has come over to visit Liz. Liz thinks that she's trying to drive a wedge between her and Peter, but Mary Jane explains that it's not like that. Her main concern is that she knows Mark is gambling again, and Liz asks that she be taken to him.
Mark immediately returns to Blackie at the Big Sky, but now the Green Goblin is with them. The Goblin explains that Mark was never in control of his armor, but was being manipulated through remote-control to think he was. Jumping on Mark's despair, the Goblin agrees to relinquish control over him if he eliminates Spider-Man, a bet he can't refuse. As if on cue, Spidey arrives at the Big Sky, and Mark immediately tears through the bar to get at him just as Mary Jane and Liz arrive and recognize him.
As the fight catches up to the present moment in time, Mark burns and tears the Big Sky to pieces, and Spidey is barely able to get the girls and Blackie to safety. Liz and Mary Jane try to get Mark to stop gambling with his life, but Mark refuses to listen and continues his assault. Spidey is eventually able to cool Mark off by spraying him with water from a fire hydrant, and the Goblin shuts off his armor in secret before flying away. Faced with the thought of her brother going away again, Liz breaks down into tears while Mary Jane and Peter try to console her. At the very least, the experience gives the girls the emotional drive during rehearsals for the school play.
Elsewhere, at ESU, Dr. Curt Conners has discovered Dr. Warren's notes on subdermal armor and is appalled. When he threatens to go to the board with the evidence, Warren calmly informs Conners that the board is already in his favor. To emphasize, Warren brings up his own damning evidence of Conners' transformation into The Lizard and tells him to keep his forked tongue quiet.
This episode provides examples of:
- Aesop Amnesia: After what happened with Electro in the second episode, you'd think Spidey would have learned his lesson about simply assuming someone's a villain and attacking. If Spider-Man had calmly talked to Mark, figured out what was going on, and taken him to see Dr. Connors, then the entire episode could have been resolved peacefully.
- Arc Words: Besides "it's a lock" to rationalize something that never actually is, there's also "I'm all in," which Mark says every time he makes a bad decision - until his final one that lands him in supervillain prison next episode.
- Blackmail:
- When Mark discovers that he cannot turn off his Molten Man abilities, not that he could in the first place. Green Goblin offers to shut down the nanites activating his powers if he can kill Spider-Man.
- Dr. Warren takes control of ESU from Dr. Conners by threatening to reveal his transformation into the Lizard.
- Blessed with Suck: Mark's Molten Man powers, once he realizes that they don't activate on HIS will, but that of the Goblin's.
- Call-Back: Dr. Warren reuses Doctor Octopus's sub-dermal armor experiment, albeit with nano-technology instead of hastily put together machines.
- Composite Character: Mark has elements of Betty Brant's brother Bennet, namely his problems with Blackie Gaxton.
- Damsel in Distress: The fight in the bar between Spidey and Molten Man is made more complicated by the fact that Liz Allan and Mary Jane Watson were in the building at the time, causing Spidey to prioritize getting them out safely. Luckily, because the girls are Mark Allen's sister and girlfriend, he allows/helps Spider-Man get them out before they resume the fight.
- Didn't See That Coming: Molten Man's fires. The Green Goblin admits that was most unexpected.
- Dynamic Entry: Goblin enters the Big Sky by loudly saying his name and his intentions, throwing a bouncer in the air, then starting a bar fight. Blackie sits through all of this as though it's a normal occurrence.
- Exact Words: Blackie and Goblin offer to clear Mark's debt if he volunteers for a little experiment. They never mention the exact details of Molten Man, which involves controlling the nanites remotely.
- Face–Heel Turn: Mark Allen, for most of the series, was a friend to Peter and a fan of Spider-Man (especially after Spidey saved Liz's life in episode 8). Here, however, his gambling gets the better of him and he ends up with an impossible choice: live as Molten Man forever or kill Spider-Man and get his life back. Out of desperation, he chooses the latter (and, thankfully, fails).
- Forced Transformation: Becoming a fire-man was the last thing Mark Allen wanted to happen to him, but too many bad choices got the better of him and led to him going "all in" on the mistake that ruined his life.
- Frothy Mugs of Water: During the bar fight, Goblin stops to drink another patron's drink. Because it's clearly a bar, the drink is supposed to be something alcoholic. However, it's colored as though it were milk.
- The Gambling Addict: Even after Mark Allen tries to leave the gambling business behind, his own selfishness and neglect pulls him right back in, with disastrous results.
- Graceful Loser: The Green Goblin takes Molten Man's defeat in stride."That's what I get for betting on an amateur."
- "Hey, You!" Haymaker:Molten Man: [to Liz] Sorry, but I'm all in.
Spider-Man: Then you leave me no choice... [kick] - How We Got Here: The episode bounces back and forth between Spidey's present fight with Molten Man and the past events leading up to it.
- Ironic Echo: "It's a lock."
- Love Triangle: Liz knows that Mary Jane would like to split up her and Peter in order to make room for Gwen.
- Mythology Gag: As in the comics, Molten Man eventually gets warm to the touch.
- Right for the Wrong Reasons: Peter arrives to Liz and Mary Jane sometime after Spider-Man beats Molten Man, or Mark. Though what he says next, she assumes it's for petty reasons.Peter: Liz! I heard about Mark at the Bugle—
Liz: PERFECT! TAKE ALL THE PICTURES YOU WANT!
Peter: That's... not why I'm here. - Space Whale Aesop: Don't gamble, kids, or you'll end up not only as a pawn in a super villain's scheme, but you'll turn into a literal fire man who burns everything he touches.
- Spotting the Thread: Dr. Warren reveals in this episode that he's connected the dots (i.e. Connors' research with lizard DNA, his sudden abandonment of the gene splicing formula, his hesitance to bring up the research again, etc) and realized that Doctor Connors was the Lizard. He uses this info, and what it could do to Connors and his wife's careers, to seize control of the ESU lab from him.
- Trapped by Gambling Debts: Mark's gambling debts lead to him being forced into a shady experiment that turns him into the Molten Man.
- Very Special Episode: Focuses on Mark's gambling addiction. Unfortunately, it shows what happens when he refuses to quit while he is ahead. Harry even takes a moment to warn Peter about a sad fact about addictions: even if he gets all of the help and support he needs, Mark has to want to stop before he can start getting better, and even then it's too easy to fall back.
