The show will pay tribute to the late Whitney Houston and Donna Summer by celebrating dance-inducing music when it airs on December 16.
Kelly Rowland and Jordin Sparks will also perform, while Adam Lambert will serve as host for the programme.
"I'm so thrilled to be hosting VH1 Divas this year," Lambert said. "I have a feeling it's going to be the most fabulous concert of the year! And LIVE!! Get ready for some amazing performances, killer fashion and fierce divas!"
The 2012 instalment of VH1 Divas will benefit the VH1 Save the Music Foundation, which is a non-profit organisation dedicated to keeping music education alive in American public schools.
Divas will air on VH1 on December 16 at 9pm/8c. Further performers will be announced in the coming weeks.
Watch the music video for Whitney Houston's 'I Wanna Dance with Somebody' below: