The pair will each take to the stage of the O2 World venue in Berlin, Germany, on November 5.
Both Robbie and Jay-Z are in the running for Best Male this year, while the rapper is also named in the Best Urban category.
Joining Robbie and Jay Z on the bill are Green Day, Leona Lewis and Tokio Hotel.
Katy Perry will host the glamorous awards after impressing bosses with her presenting skills last year.
A source said: Katy - who hosted the awards in style last year as she rode on a giant chapstick and cherries and dazzled with her costume changes - is the only artist ever to be asked to host two successive shows in the 15-year history of the MTV Europe Music Awards.
More performers are to be announced in the coming weeks.
Lady Gaga and Kings of Leon lead the nominations with five nods each.
