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.

Introducing Characters: The Sinister Six (Electro, Doctor Octopus, Shocker, the Vulture, Sandman, and Rhino) and Dr. Ashley Kafka

Note: Beginning with this episode, all episodes left in this season aired on The CW4Kids (formerly called Kids' WB).