All villains in Sam Raimi's Spider-Man trilogy learned the web-slinger's identity, either because he unmasked himself or through other methods.
Spider-Man is one of those superheroes who do his best to keep his identity a secret for the safety of his loved ones, but in Sam Raimi’s Spider-Man trilogy, the villains that Tobey Maguire’s Spider-Man came across ended up discovering his identity in different ways.
Norman Osborn/Green Goblin Norman Osborn was the father of Peter’s best friend, Harry, and he was a scientist and the founder and owner of Oscorp, a multi billion-dollar multinational corporation. Norman wanted to secure an important military contract, so he experimented on himself with a performance-enhancing chemical that was actually quite unstable, and the experiment didn’t go well.
Doctor Octopus Spider-Man 2 introduced Doctor Otto Octavius, a nuclear scientist working on behalf of Oscorp and Peter’s role model. Oscorp, now led by Harry, was financing Octavius’ fusion power project, but a public demonstration went horribly wrong.
Harry Osborn/New Goblin As Harry saw Spider-Man leave Norman’s dead body at his house, he blamed the web-slinger for his father’s death and swore vengeance against him. Harry actually learned Spider-Man’s identity before his transformation into a villain, as it happened in Spider-Man 2 and he became the New Goblin in Spider-Man 3.
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