The trio will hand out accolades at the ceremony on June 3 at Los Angeles' Gibson Amphitheatre in Universal City along with 'The Amazing Spider-Man' co-stars Emma Stone and Andrew Garfield, as well as Charlize Theron, Michael Fassbender, and Mark Wahlberg.
'The Hunger Games' and 'Bridesmaids' lead the nominations at the 2012 MTV Movie Awards with eight nods apiece, and they will go up against each other for Movie of the Year, Best Cast and Best Female Performance thanks to Jennifer Lawrence and Kristin Wiig being nominated.
The acting pair, along with Melissa McCarthy, all received four nominations, while their nearest female rivals, Emma Stone, Emma Watson, and Rooney Mara have three nods apiece.
Channing Tatum, Jonah Hill and Josh Hutcherson are also up for three prizes each, with Channing and Josh set to face-off for the Best Male Performance gong along with Daniel Radcliffe, Ryan Gosling, and Joseph Gordon-Levitt.
A number of new categories will feature at this year's event, including Best On-Screen Dirtbag, which sees Bryce Dallas Howard, Jennifer Aniston, Colin Farrell, Oliver Cooper and Jon Hamm all nominated.
British TV host and fashion expert Louise Roe will return as MTV's international guest correspondent for the 2012 MTV Movie Awards, which will be screened on Monday June 4 on MTV at 9pm.
Voting for the accolades takes place at MovieAwards.MTV.com until June 2.