Justin Timberlake and Jay-Z were named on Tuesday by live music promoter Live Nation Entertainment as headline acts for the Wireless Festival on July 12 and July 13.
Other acts will include Snoop Dogg, John Legend, Frank Ocean, Emeli Sande, Rita Ora, and DJ Calvin Harris.
Last month Live Nation said it had secured exclusive rights in 2013 to host concerts in the Olympic Park and Stadium complex in east London that was designed so it could be transformed into a space for entertainment, leisure and work after the Games.
The announcement was a boost for the British government which pumped public money into the London 2012 Games, adamant the Olympic site would not become an expensive white elephant.
"This is a stellar line up of stars that is set to bring the house down this summer at Queen Elizabeth Park London. It proves that our fantastic Olympic park is now a destination of choice for world class musical events," London Mayor Boris Johnson said in a statement.
Live Nation said this would be Jay-Z's only European show this year and Timberlake's sole British festival appearance.
Earlier this month the two U.S. singers appeared together at the Grammys to perform their collaboration "Suit & Tie" off Timberlake's first new album in seven years that is due out on March 18.
Live Nation plans to hold the Wireless Festival and Hard Rock Calling events at the Queen Elizabeth Olympic Park and avoid a repeat of previous years when the concerts were staged in London parks and triggered complaints from nearby residents.
Concert-goers were surprised in July when microphones were suddenly switched off on Paul McCartney and Bruce Springsteen in mid-duet when a Hyde Park concert ran over time.
(Reporting by Belinda Goldsmith, editing by Paul Casciato)