Daniel Craig will appear in a special James Bond sketch for Comic Relief, to be broadcast as part of Red Nose Day on March 13.
The skit will feature in Face the Funny, the charity’s first show to be broadcast live from the London Palladium.
Professor Stephen Hawking will appear in a new Little Britain sketch, featuring David Walliams as carer Lou.
The physicist will take Matt Lucas’s role as the fake wheelchair-bound Andy.
It is the second Comic Relief sketch for Daniel Craig, who is currently filming new James Bond movie Spectre.
Daniel Craig appeared in a sketch with Catherine Tate in 2009, which saw her character Elaine Figgis dating a spy played by the actor.
Stephen Hawking’s Little Britain cameo follows Kate Moss’ appearance during a Comic Relief show at Hammersmith Apollo in 2006, when she joined Matt Lucas on stage as Katie Pollard, the sister of Vicky Pollard.
Other previously announced sketches to feature during this year’s charity appeal include Rowan Atkinson’s return as Mr. Bean, Dawn French in the Vicar of Dibley and highlights of Peter Kay’s live Phoenix Nights show.
John Bishop, Eddie Izzard, Davina McCall and David Walliams will also take to the stage for a reinvention of Monty Python’s Four Yorkshiremen sketch.
Dermot O’Leary will complete his 24-hour dance marathon live at the London Palladium.