(at around 24 mins) When Peter flips over an oncoming car, Tobey Maguire performed the stunt himself. A stuntman also performed it, but Sam Raimi thought Maguire's looked more natural so he used his instead.
The train fight between Doc Ock and Spider-Man was the idea of director Sam Raimi and the first major sequence to be filmed.
Costume designer James Acheson made subtle changes to Spider-Man's costume from the previous film. The colours were made richer and bolder; the spider emblem was given more elegant lines; the muscle suit underneath was made into pieces, to give a better sense of movement; and the helmet Tobey Maguire wore under his mask was also improved, adding a false jaw for better movement and magnetic eyepieces which were easier to remove.
For the sequence where Aunt May is taken hostage and later aids Spider-Man, Rosemary Harris performed the action scenes herself.
If you look closely at Peter's apartment, you can see the picture he took of Mary-Jane just before he was bitten by a genetically altered spider. It was supposed to represent the last moment of innocence in Peter's life before it changed forever.
Weston Epp, Jopaul Van Epp: (at around 1h 40 mins) The two boys who hand Spider-Man his mask on the train are Tobey Maguire's half-brothers.
Hal Sparks: (at around 29 mins) The man who meets Spider-Man inside the elevator (and compliments him on his Spidey outfit) is "Michael Novotny" from Queer as Folk (2000), a gay man obsessed with comics and superheroes, who'd always dreamed of meeting one on the show. An alternative version of this scene was used in the Spider-Man 2.1 cut of the film (at around 32 mins).
Scott Spiegel: screenwriter of Sam Raimi's L'opéra de la terreur 2 (1987) is the man on the balcony who tries to eat a piece of pizza.
John Landis: one of the doctors killed in the "birth of Doc Ock" sequence. This is also the second time he plays a doctor in a Sam Raimi film, the first one being Darkman (1990).
Sam Raimi: (at around 9 mins) near the beginning of the movie, when Peter is on campus, he drops his books. When he bends down to retrieve them, he is hit in the head by two backpacks. Raimi, whose face is not seen, is the second "student" to hit him.
Sam Raimi: [POV shot] (at around 41 mins) The view from Dr. Octopus' tentacles attacking the doctors operating on him, which Raimi called "Octovision".
Sam Raimi: [car] (at around 1h 10 mins) Raimi's 1973 Oldsmobile Delta 88 car, nicknamed The Classic, sits in Aunt May's driveway.
Sam Raimi: [screaming woman] When Doc Ock and Spider-man are fighting after the bank robbery, a blonde woman sees Doc Ock and flees toward the camera, stops in front of it, looks directly into it and screams. This is a common occurrence in Raimi's films to convey fear, especially horror films.
Sam Raimi: [internal conflict] When Octavius laments that Peter was correct about misinterpreting the calculations, the camera POV suddenly shift to behind him. He then faces the camera in an angry state, looking radically different - far more haggard and frightening. This "mirror image" of Octavius shows his sinister side, and is a common occurrence in Raimi's films. Notably, it occurred in the previous film when Norman Osborn argued with himself in the mirror.