The iconic star will play the main stage on Sunday, June 17 and will precede headliner Grace Jones along with disco legends Chic.
Lovebox music festival will celebrate its 10th anniversary in 2012 and will return to London's Victoria Park across the weekend July 15-17.
Friendly Fires and Hot Chip have been confirmed as the other two headliners, while Emeli Sandé, Kelis, Stooshe, Lana Del Rey, Rita Ora, Azari & III and Madeon will also play sets.
Tickets for the three-day event are on sale now and can be purchased through the festival's official website.
Watch Chaka Khan perform 'Ain't Nobody' below: