Daniel Craig and former 007 Sir Roger Moore will be joined by some of the current crop of stars from the films including Ben Whishaw, Rory Kinnear, Naomie Harris and director Sam Mendes.
Mendes said: “I decided to take part in this sketch because the work Comic Relief undertakes, especially in west Africa, for people whose suffering is beyond our comprehension is truly exceptional. Any help I can offer, even in the smallest of ways, is a privilege.”
The mockumentary-style sketch, written by David Walliams and his Big School collaborators the Dawson Brothers, will see Craig reveal a Bond bombshell to shock fans.
Sir Roger said: “I think viewers will most enjoy seeing that old Bonds never die.”
The sketch will be shown as part of tonight’s Comic Relief which starts at 7pm on BBC1.
The broadcast comes as Mexican actress Stephanie Sigman was anounced as the latest cast addition to forthcoming Bond movie Spectre, joining previously announced stars Monica Bellucci and Lea Seydoux.
The news was announced on the official James Bond Twitter account.