The World War Z star, who is a potential nominee for next year's award ceremony, will be handing the golden popcorn to either The Avengers, The Dark Knight Rises, Django Unchained, Silver Linings Playbook or Ted.
Brad is three for eight in terms of MTV Movie Award wins, taking home the statuette for Best Male Performance in 1995 for Interview with the Vampire, Most Desirable Male in 1996 for Se7en and Best Fight in 2006 for Mr. & Mrs. Smith. The latter he shared with fiancee Angelina Jolie.
Rebel Wilson will host the event broadcasting live from Los Angeles on Sunday, April 14 at 9 p.m. ET/PT on MTV.
Other presenters include Zac Efron, Melissa McCarthy, Chris Rock, Chris Pine, Zoe Saldana, Zachary Quinto and Peter Dinklage.