The singer will play her only live UK date of 2012 at the London-based music event on July 8 at Hyde Park.
The Bajan star will perform at the final night of the festival which will run between July 6-8, with the other two headliners to be announced in due course.
The one-off 2012 date follows the 23-year-old's current sold-out UK tour, which will see her play a record-breaking ten dates at London's O2 Arena.
Rihanna's sixth studio album Talk That Talk is released on November 21, while her new single 'We Found Love' has already topped the UK and US charts.
Tickets for Wireless Festival go on sale on November 18 from 9am.
The Wireless 2011 lineup included the Black Eyed Peas, The Chemical Brothers and Pulp.
> Rihanna's 'Talk That Talk' contains four chart smashes, says producer
> Rihanna rides the Tube to London O2 Arena gig - video
Watch behind-the-scenes footage of Rihanna's 'Loud' tour below: