The concert, which will take place on the evening of Friday June 27, is being staged as a celebration of Mandela's 90th birthday.
Those set to perform include Leona Lewis, Annie Lennox, Razorlight, Dame Shirley Bassey and Simple Minds. Further headline acts are being lined-up as special, surprise guest appearances.
Hollywood film star Will Smith and other, as yet unannounced, celebrities will introduce the acts on stage.
Phillip Schofield will host the "as live" coverage for ITV1, while Fearne Cotton will be reporting from backstage and interviewing the artists.
The event is being set up by 46664, Nelson Mandela's global HIV/Aids awareness campaign, after he chose London for his 90th birthday celebrations.
Guy Freeman, controller of ITV Music and Events, said: "Nelson Mandela coming to London to celebrate his 90th Birthday is about as good a reason as it gets for having a party.
"This will be such an exciting, historical event with an amazing line-up of artists already taking part and I'm delighted that it's on ITV1."