- Captain America (Steve Rogers) (First full appearance)
- Aunt May Parker (Cameo)
- J. Jonah Jameson (Appears on a computer screen, TV, or hologram only) (Vision)
- The Avengers
- Captain America's Shield
- Spider-Man's Web-Shooters
- Nova Helmet
- White Tiger Amulet
- Doctor Doom's Armor
- Doom Dogs
- S.H.I.E.L.D. Helicarrier
- Latverian Jet
Spider-Man and the team having a friendly training session with Captain America on board the Helicarrier. He shows the young heroes how to fight and that training and skill can beat any opponent with enough practice. When Coulson comes in to speak with Cap wearing a Captain America T-shirt, he is revealed to be his biggest fan and was shocked when he knew his name. He leaves his shield for the team to look at stating that "It is not a toy". While handling Captain America's Shield, Spider-Man accidentally throws it out of the window, he jumps after as it hurtles thought Iron Man's head and the city taking out the Trapster on the way. The shield lands in the Latverian Embassy, where it is found by Doctor Doom.
Spider-Man is met by Captain America who decides to try and sneak into the embassy and retrieve the shield before Doctor Doom has a chance to exploit it for his own nefarious purposes. They have to fight pass lasers and a horde of Doombots, even a pack of Doom Dogs. Later, in the Embassy, they learn that Doom had plans to attack various targets across the United States. Cap deactivates the Doombots using Doom's computers and goes after Doom who was escaping in a craft on the roof. They are attacked by another pack of Doom Dogs and missiles. After a short battle they web Doom's craft and smash it through the screen, but Cap is hit by his own shield. They land in Central Park, and Doom blasts the two heroes, who manage to dodge the attack. No longer on Latverian soil he is forced to return the shield as a S.H.I.E.L.D. agent escort him away.
On the Helicarrier, Coulson scolds Spider-Man for losing the shield. But when Cap asks Coulson to pass him, the shield accidentally flies out the Helicarrier once more and Spider-Man chases after it again .
- When Captain America says that he doesn't dd well to sidekicks, he is referencing Bucky's (apparent) demise.