The outdoor gig will feature acts from all four nations in the UK, with Duran Duran representing England.
Wales will be represented by Stereophonics, Snow Patrol will play for Northern Ireland and Paolo Nuttini will appear for Scotland.
Simon Le Bon, Duran Duran’s lead singer, said: “Performing to so many people on the most exciting day in sport for Great Britain will be one of the highlights of the last decade for us.
“We have been invited to represent England for this Team GB show, and we couldn’t be more proud. Seeing the torch being lit on the big screens before hitting the stage in this iconic location will be a great experience… we simply can’t wait”.
The concert will coincide with the Olympics opening ceremony on July 27, which will be shown on screens in the park between performances.
The opening ceremony will also be broadcast onto two giant screens in Victoria Park in Tower Hamlets.
Tickets for the celebration concert go on sale on May 4 at 9am.
Another major outdoor show in Hyde Park, with Blur as the main act, will mark the closing ceremony on August 12.
The “Best of British” themed line up will also feature New Order and The Specials.