The singer will join a lineup consisting of Olly Murs, The Wanted and Pixie Lott at the festive concert, which will take place on December 3 and 4.
Calvin Harris and Jason Derulo have also been confirmed for performance slots at the annual show at London's O2 Arena.
Rihanna's set at the O2 will be her 11th this year, as the star managed to sell out a record-breaking ten dates at the venue as part of her 'Loud' world tour.
Tickets for the first day of the two-day event are on sale now. The Jingle Bell Ball's second day of acts will be unveiled soon.
Last year's lineup featured sets from Kylie Minogue, JLS, Tinie Tempah and The Saturdays.
Meanwhile, Rihanna is currently preparing to release her sixth studio album Talk That Talk on November 21.
Watch the music video for Rihanna and Calvin Harris's new single 'We Found Love' below: