Tobey Maguire Spider-Man / Peter Parker Kirsten Dunst Mary Jane Watson James Franco Harry Osborn Alfred Molina Doc Ock / Otto Octavius Rosemary Harris May Parker J.K. Simmons J. Jonah Jameson Donna Murphy Rosalie Octavius Daniel Gillies John Jameson Dylan Baker Dr. Curt Connors Bill Nunn Joseph 'Robbie' Robertson Vanessa Ferlito Louise Aasif Mandvi Mr. Aziz Willem Dafoe Green Goblin / Norman Osborn Cliff Robertson Ben Parker Ted Raimi Hoffman Elizabeth Banks Miss Brant Bruce Campbell Snooty Usher Gregg Edelman Dr. Davis Elya Baskin Mr. Ditkovitch Mageina Tovah Ursula Daniel Dae Kim Raymond Hal Sparks Elevator Passenger Joel McHale Mr. Jacks Stan Lee Man Dodging Debris Kelly Connell Dr. Isaacs Brent Briscoe Garbage Man Emily Deschanel Receptionist Scott Spiegel Man on Balcony Christine Estabrook Mrs. Jameson Molly Cheek Society Woman John Paxton Houseman Joy Bryant Woman at Web Joanne Baron Skeptical Scientist Peter McRobbie OsCorp Representative Timothy Jerome Injured Scientist Taylor Gilbert Mrs. Watson Peter Vouras Stage Manager Donnell Rawlings Pizza 'Heist' Witness Louis Lombardi Poker Player Marc John Jefferies Amazed Kid John Landis Doctor Tom Carey Train Conductor Joey Diaz Train Passenger Timothy Patrick Quill Train Passenger Phil LaMarr Train Passenger (uncredited) Peyton List Little Girl Playing on Steps (uncredited)