Charlie will introduce a tribute to party films and will announce musical act Wiz Khalifa, who was recently arrested for marijuana possession.
A source told E! News: "Even though Charlie has cleaned up his act, he still has a sense of humor about his out-of-control days."
Another source said: "It's all going to be a really big party moment."
Also at the event on Sunday night Kristen Stewart will present a section with her 'Snow White and the Huntsman' co-star Chris Hemsworth.
Meanwhile her boyfriend and Twilight Saga: Breaking Dawn - Part 2 co-star Robert Pattinson will not be attending this year.
Russell Brand will host the bash.
The British comedian - who announced his divorce from Katy Perry last December - will present the June 3 ceremony at the Gibson Amphitheatre in Universal City, California, for the first time, and he insists the event will be "more impressive" than recent box office sensation 'Avengers Assemble'.
He said: "This MTV Movie Awards will be more impressive than 'The Avengers' and you won't have to wait an hour for someone to Hulk out."