The veteran American actor and director will lead a nine-member jury for the May 11-22 festival on the French Riviera.
De Niro's charisma may provide a Hollywood boost to Cannes. Last year's event was lighter than usual on star power and featured a lineup that left many critics unimpressed.
The Thai film Uncle Boonmee Who Can Recall His Past Lives won the top honor at the 2010 festival, while Academy Award winners Juliette Binoche and Javier Bardem earned acting honors.
De Niro said he felt honored by the invitation, calling it "a rare opportunity," Cannes organizers said in a statement.