Stereophonics, Snow Patrol and Paolo Nutini will also take to the stage in Hyde Park for the gig on Friday, July 27.
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The four acts have been chosen to represent the home nations of the United Kingdom - England, Wales, Northern Ireland and Scotland.
Simon Le Bon of Duran Duran said in a statement: "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".
Snow Patrol's Johnny Quinn said that the invite to perform was "an honour", adding: "I think it will be very special."
The performers will play as part of the opening ceremony celebration - with 60,000 fans expected to turn out - with performances timed around the live broadcast of the Olympics opening ceremony on the BBC.
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Blur have already been confirmed to headline another BT event - held at the same location - to recognise the closing ceremonies.
Blur will play Hyde Park on Sunday, August 12 with support from The Specials and New Order, and bassist Alex James has revealed that the band will perform a new "tear-jerker" at the show.
The band have previously promised that the shows will be even better than their first reunion gigs three years ago, with James saying: "I think the reunion shows we did in 2009 are the best we've ever done, so this is exciting."
Frontman Damon Albarn told NME when the show was announced: "Hopefully it won't take quite as long to learn all the songs again this time."
Tickets for the BT London Live Olympics opening ceremony celebration go on sale to BT customers on Thursday (May 3), followed by a general sale on May 4.
Watch Duran Duran performing 'Hungry Like the Wolf' at Coachella 2011 below: