The 1980s rockers will represent England at the BT London Live concert on July 27, sharing a stage with Welsh band Stereophonics, Northern Ireland's Snow Patrol and Scottish singer Paolo Nutini.
Concertgoers will be able to watch the opening ceremony live on giant screens.
Organisers said the performances would be timed so the audience at the concert will be able to watch TV coverage of the opening ceremony from the Olympic Park.
A sold-out concert headlined by Britpop band Blur will be held to coincide with the Games' closing ceremony on August 12.
Britain doubled its budget for the opening and closing ceremonies in December to £81 million ($131 million, 99 million euros).
The theme of the opening extravaganza, directed by Oscar-winning filmmaker Danny Boyle, will be "Isles of Wonder", inspired by a passage from William Shakespeare's comedy "The Tempest".