The two pop stars have been confirmed to take to the stage at the Nokia Theater in Los Angeles this Sunday (13.04.14), where they will sing their number one hit single, 'The Monster'.
The performance will be a precursor to their US summer stadium tour of the same name, which will take them to LA, New Jersey and Detroit.
Eminem and Rihanna, who previously collaborated on two versions of 'Love The Way You Lie', achieved international success with the latest single taken from the rapper's 'The Marshall Mathers LP 2'.
The rapper and the R&B superstar join previously announced acts on the line-up including Twenty One Pilots, who are set to play their new single 'Car Radio', and Ellie Goulding and Zedd, who are teaming up to sing 'Beating Heart' and 'Find You'.
The 2014 MTV Movie Awards are going to be hosted by Conan O'Brien and aired live from 9pm on April 13.
Conan, who is known for his self-deprecating humour, will be at hand to deliver the coveted golden popcorn statuettes to this year's winners from the world of film.
He also gets to meet his long-lost twin brother Dru.
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