The Descendants actress will play the web-slinger's love interest Mary Jane Watson, the character portrayed by Kirsten Dunst in previous Spidey films, and told MTV she can't wait to work with director Mark Webb and co-stars Andrew Garfield and Emma Stone.
She told MTV: "I think Marc Webb is amazing. I'm so stoked to work with Andrew and Emma.
"They're the best of the best."
Shailene said she has always been a fan of the story.
" Spider-Man's always been my favourite superhero since I was a little girl," she said.
"I always thought there was something special about flying. When I watched the previous Spider-Man with Andrew Garfield, he made me feel invincible. I also cried when Uncle Ben died. I knew it was coming, and I still cried!"
The upcoming movie will see Andrew reprise his role as Peter Parker and his superhero alter-ego, while Emma will be back as Gwen Stacy. Jamie Foxx is thought to be starring as super villain Electro.
Production is set to begin early this year, for a release in May 2014.