Peter Parker and Mary Jane Watson
Mary Jane wants to start a relationship with Peter, who still resists because he fears for her safety. In her frustration Mary Jane goes on to have a relationship with John Jameson (Daniel Gillies), the astronaut son of Daily Bugle publisher J. Jonah Jameson (J.K. Simmons). Prior to this, Harry said that she was waiting for him. Much to Peter's delight, he sees her billboard picturing her modeling for a perfume near the pizza place he works at.
Later, Peter decides that being Spider-Man is not what he wants and he attempts to start a relationship with her. Mary Jane pushes him away this time because she is getting married to John Jameson, but secretly does want a relationship with Peter, although she tries to convince herself otherwise. She is also angry at Peter because he fails to see her star in The Importance of Being Earnest, which John, Harry, and Aunt May have seen, some of them more than once. (Even her father went backstage to ask for money.) When Peter does arrive to see it the first time, a snooty usher (Bruce Campbell) stops him for being late. The second attempt to see it, which is successful, is when he tries to reconnect with her. After Mary Jane kisses John, in a manner that is reminiscent of the upside-down kiss between she and Spider-Man from the first film, she finds that she may want a relationship with Peter.
She meets Peter in a coffee shop where she asks for a kiss to confirm her belief that he is Spider-Man. She even asks him if he loves her, to which he falsely replies,"I don't", for the sake of his superhero responsibilities and her safety. Just before Peter can kiss her, Doctor Octopus (Alfred Molina) kidnaps her and runs away. Doctor Octopus takes her to an abandoned pier where Spider-Man confronts him. Spider-Man pulls his mask off in hopes of getting Doctor Octopus to come back to his senses, and Mary Jane sees that Spider-Man and Peter Parker are one and the same. After Doctor Octopus reforms and sacrifices himself to save New York, Spider-Man and Mary Jane share a moment toegther, where Spider-Man finally admits that he does love Mary Jane, but cares more for her safety.
At the film's end, Mary Jane prepares to marry John Jameson, but she leaves him at the altar, goes to Peter's apartment, and reveals that she loves Peter and is prepared to face whatever risks their relationship may bring.