Twilight co-stars Kristen Stewart and Robert Pattinson were the toast of the evening as they both triumphed in the Best Female and Male Performance categories.
The rumoured real-life lovers also shared the prize for Best Kiss, and teased the crowd by debating whether or not to follow tradition with a live lip-lock. But Stewart let viewers down by snubbing a Pattinson smooch, declaring: "To be perfectly honest with you, it takes a lot of smoke and mirrors to make us look good kissing."
Pattinson was also dubbed the night's Global Superstar.
Other MTV Movie Award winners included Anna Kendrick, who was named the Best Breakout Star, accepting the prize for her role in Up in the Air, opposite George Clooney; meanwhile, The Hangover stars Zach Galifianakis and Ken Jeong won for Best Comedic Performance and Best WTF Moment, respectively.
But it was Sandra Bullock's return to the spotlight that really got audiences revved up as she accepted the MTV Generation Award.
The Oscar winner, who stepped away from the public eye in the weeks after her husband Jesse James' infidelity was exposed in the press, was welcomed to the stage with a standing ovation after an introduction by Bradley Cooper, Betty White and Scarlett Johansson - who unexpectedly planted a kiss on the actress.
Bullock laughed off rumours she plans to quit acting, and made light of her personal life, telling the crowd: "Now that we have done that (kissed), can we please go back to normal? Because therapy is really expensive."
The evening also featured a series of hilarious skits starring Tom Cruise as his foul-mouthed, bad-tempered Tropic Thunder character Les Grossman - including a performance with a group of scantily clad backing dancers and a surprise duet with Jennifer Lopez.
Katy Perry and Snoop Dogg took the stage to perform her track California Gurls, while Christina Aguilera closed the show by debuting a medley of songs from her new album Bionic.
The 2010 MTV Movie Awards winners are as follows:
Best Fight - Beyonce Knowles & Ali Larter (Obsessed)
Best Female Performance - Kristen Stewart (The Twilight Saga: New Moon)
Best Breakout Star - Anna Kendrick (Up in the Air)
Best Scared-As-S**t Performance - Amanda Seyfried (Jennifer's Body)
Best Kiss - Kristen Stewart & Robert Pattinson (The Twilight Saga: New Moon)
MTV Generation Award - Sandra Bullock
Best Comedic Performance: Zach Galifianakis (The Hangover)
Global Superstar Winner: Robert Pattinson
Best WTF Moment - Ken Jeong (The Hangover)
Best Movie Villain - Tom Felton (Harry Potter and the Half-Blood Prince)
Biggest Bada** Star - Rain (Ninja Assassin)
Best Male Performance - Robert Pattinson (The Twilight Saga: New Moon)
Best Movie: The Twilight Saga: New Moon.