Starring Kristen Stewart, Jesse Eisenberg and Steve Carell, the movie centres on the buzzing cafe society of 1930s Hollywood.
It makes Allen the first director to present three opening-night films at Cannes.
Hollywood Ending opened the annual festival in 2002, and Midnight in Paris in 2011.
According to the festival organisers, Cafe Society tells the story “of a young man who arrives in Hollywood during the 1930s hoping to work in the film industry, falls in love, and finds himself swept up in the vibrant cafe society that defined the spirit of the age”.
It marks a romantic reunion for Stewart and Eisenberg who appeared together in American Ultra.
Cafe Society will screen out of competition at this year’s event, which runs from 11 to 22 May, ahead of its release later this year.
Jodie Foster’s Money Monster starring Julia Roberts and George Clooney, and Steven Spielberg’s The BFG are already confirmed to screen at the festival.
The full official selection will be announced mid-April.