| ShortSummary | - On Valentine’s Day, Peter Parker jeopardizes his relationship with girlfriend Liz Allan, when Tombstone, Doctor Octopus and Silvermane call a Valentine’s Day Summit. But when Hammerhead betrays them all in an attempt to become the new Big Man, the summit erupts into a gang war – one only Spider-Man can stop!
- While Peter takes on the responsibility of helping Aunt May pay the bills, Montana becomes the stunning Shocker to fulfill his responsibility: eliminating Spider-Man.
- Spider-Man volunteers to try to escape the Vault in order to test the security system. But the Green Goblin has other ideas, trapping Spidey inside Ryker’s amid a sea of felons he put away.
- Peter Parker and Spider-Man both must learn to own their choices when decisions made by Dr. Curt Connors transform Pete's mentor into The Lizard.
- Some days, Peter Parker just can’t win… especially when he winds up on a Midtown High police car ride-along with Sally Avril. As Spider-Man, his luck isn’t any better, facing off against Shocker, Ricochet and Ox the new Enforcers.
- With Electro's help, Doctor Octopus breaks himself, Vulture, Sandman, Rhino and Shocker out of Ryker's Island prison to quench their mutual thirst for revenge. Even with his new black alien suit, Spider-Man finds his old enemies, now called the Sinister Six, are more than he can handle.
Note: Beginning with this episode, all episodes left in this season aired on The CW4Kids .
- Venom is back and framing Spider-Man. Meanwhile, alien spores infect John Jameson, increasing his size, strength and mass. J. Jonah Jameson convinces his son to become a superhero, to capture Spidey...
- On the night of the Midtown High Fall Formal, Peter's date, Mary Jane Watson, threatens to invert Midtown's social structure. Elsewhere, the mysterious, murderous Green Goblin tries to force L. Thompson Lincoln to step down as NYC's Big Man of crime. Will Spider-Man be able to take this new threat seriously enough – or will he be so cocky that he loses his big head?!
- When Spider-Man defeats another Goblin squad, he wonders where the Green Goblin could really be. When Peter reaches home, Gwen calls him, telling him that she needs Peter's help. Peter arrives at Gwen's home and finds Harry. Harry told them the whole story why he has been missing in the past few days, and that he isn't the Goblin. Peter Parker as Spider-Man reaches the Oscorp tower, and fights the Green Goblin who he once thought it was Norman Osborn. When Peter breaks up with Liz Allan, he returns to Oscorp to get the address of Donald Menkin. The Goblin showed up, but when Spider-Man unmasked him, he turns out to be Norman Osborn. Chameleon was working with him all along. After the battle, Norman was thought to be dead until he shows up somewhere in an airport.
- School’s back in session, and things have changed. Peter Parker’s actually invited to Flash Thompson’s birthday bash. Meanwhile, Spider-Man has to party with Sandman, who’s once again looking to make his Big Score. And is that Venom disappearing into the night?
Note: Frog-Man and his henchmen make an appearance working for Hammerhead.
- As Christmas approaches, the Sinister Six reconstitutes with Sandman, Rhino, Vulture, Electro and new members Mysterio and Kraven. All they want for Christmas is Spider-Man – dead. Meanwhile, Peter Parker finds his wandering eye prevents him from being with Gwen Stacy. He’ll have to learn to focus if he wants to get the girl… and if he wants to stay alive.
Note: Patch makes his first appearance in the series.
- Peter is in a celebratory mood as Aunt May is released from hospital, but Eddie Brock has no intention of letting them have a happy reunion. Can Spider-Man defeat his new arch-nemesis?
- Determined to be a better boyfriend to Liz Allan, Peter Parker wishes he could help her brother Mark Allan. But when Green Goblin turns Mark into Molten Man and blackmails him into doing his bidding, neither Liz, Mary Jane Watson nor Spider-Man may be able to save him!
- Peter Parker attempts to tutor the popular Liz Allan while Spider-Man tries to stop Electro, who will stop at nothing to find a cure for the accident that made him who he is.
- A gang war looms as Silver Sable, Hammerhead, and Doctor Octopus vie for a prize that could change the balance of power in the New York Underworld.
Note: Fredrick Foswell is revealed as Patch, and Roderick Kingsley makes an appearance.
- While Colonel John Jameson struggles to land his damaged space shuttle, Spider-Man struggles to defeat the Green Goblin, who also threatens Hammerhead and Tombstone. But Peter Parker's biggest challenge will be facing the truth when he finally learns the Goblin's "true" identity, all on Halloween!
- Note: Stan Lee makes a brief appearance in this episode.
- Peter Parker struggles to get a date for the Fall Formal, and to figure out a way to pay for it. Meanwhile, the unstoppable Rhino – the latest of the Big Man's creations – has sworn vengeance on Spider-Man. Spidey takes the battle directly to the source of his troubles, the previously invisible hand, who has been secretly conducting his villain-of-the-week attacks. But the Big Man offers a surprising solution to Spidey's problems, a tempting offer he doesn't think our hero can afford to refuse. Will Spidey do the right thing?
- Spider-Man gains a black costume, courtesy of the alien life form, during an encounter with the Black Cat. Meanwhile, a master of disguise, the Chameleon, starts framing Spidey for various robberies, using inventions and effects provided by Quentin Beck and Phineas Mason. Spider-Man is left with no option but to team up with Black Cat to stop his new enemy's crime spree.
- Peter Parker and Spider-Man learn that actions have consequences when nebbishy Dr. Otto Octavius becomes the megalomaniacal Doctor Octopus. The cause: Green Goblin; the effect: Mayhem!
- It’s early December, and the first snow is falling. Peter Parker has a long “To Do” list – leading off with talking to Gwen Stacy about their surprise first kiss. But before he gets the chance, Spider-Man has a run-in with the "sorcerer" Mysterio.
Note: Starting with this episode, all episodes began to air on Disney XD in the USA.
- Summer is over for Peter Parker and school's ready to start -- both literally , and in the real world of crime-fighting -- as Spider-Man faces his first real challenge The Enforcers and his first real super-villain Vulture.
- Peter Parker’s secret identity as Spider-Man has been outed by Venom, leaving Pete and his loved ones vulnerable to all of Spidey’s enemies.
- With Aunt May in hospital and his friendship with Eddie Brock ruined, Peter finally gains enough self-awareness to realize the alien symbiote is starting to affect his personality. The struggle between Peter and the symbiote evolves into a war within Spidey's own mind, where Pete is aided by a familiar face.
- As Peter Parker and Harry Osborn try out for the football team, Spider-Man must face convict Flint Marko, newly transformed into the Sandman in order to destroy Spider-Man.
- Both Gwen Stacy and Liz Allan like Peter Parker. So whom should Pete pursue? Meanwhile, Kraven the Hunter has come to New York to make Spider-Man his prey!
- It’s New Year’s Eve, and the Master Planner and his henchmen are literally planning to take over the world! A highly motivated Spider-Man takes the fight to the Planner’s secret lair, but once he gets there, can he survive?
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