It is believed that Spider-Man 4 could be the last outing for her character, Mary Jane Watson, who featured as Peter Parker's love interest in the first three films.
A source told Star magazine: "The plan is for her character to be written out, probably by dying.
"Anne will take over as Peter Parker's new love interest for this project and for Spider-Man 5 and Spider-Man 6 which are being written now.
"Anne's in L.A. doing a lot of meetings on the movie because filming is right around the corner."
Hathaway is rumoured to be playing the part of Felicia Hardy, known as Black Cat in the Marvel comic series but thought to go by the name Vultress in the film adaptation.
Filming on Spider-Man 4, directed by Sam Raimi and starring Tobey Maguire, is still expected to begin early next year for a May 5, 2011 release date.