Rap superstar Wiz Khalifa will perform his new single "Work Hard, Play Hard" for the first time on television at the 2012 MTV Movie Awards.

Khalifa joins chart-topping indie-pop group Fun. as the second performer announced for the annual Golden Popcorn-fest. "Work Hard, Play Hard" is the debut single from the Pittsburgh rapper's hotly awaited second studio album, O.N.I.F.C., which will hit stores in August.

In addition to Khalifa, several of the biggest stars in film have been added to the lineup of presenters for the big show. "That's My Boy" co-stars Adam Sandler and Andy Samberg, "Gossip Girl" diva Leighton Meester and "Perks of Being a Wallflower" castmates Emma Watson, Logan Lerman and Ezra Miller will join already-announced presenters Emma Stone, Andrew Garfield, Kristen Stewart, Chris Hemsworth, Charlize Theron, Michael Fassbender, Mila Kunis and Mark Wahlberg at the Russell Brand-hosted event.

Watson, Lerman and Miller will also be on hand during the Movie Awards pre-show to debut the first "Perks" trailer. "The Perks of Being a Wallflower," based on the popular Stephen Chbosky novel of the same name, tells the story of introverted high school freshman Charlie (Lerman) as he slowly comes out of his shell thanks to new friends, siblings Sam (Watson) and Patrick (Miller).

The 2012 MTV Movie Awards will air live on MTV from the Gibson Amphitheatre in Universal City, California, on Sunday, June 3 at 9 p.m. ET/PT.

Head over to MovieAwards.MTV.com to vote for your favorite flicks now! The 21st annual MTV Movie Awards air live Sunday, June 3, at 9 p.m. ET.