The 10th anniversary of the fundraiser for her Keep a Child Alive charity will take place at the Hammerstein Ballroom in New York City.
British soul star Laura Mvula and opera singer Kathleen Battle will also perform.
Keys says, "This year's Black Ball is particularly special for all of us at Kca because it's a celebration of our 10th anniversary.
"It's incredible the impact that we've been able to make since the beginning. I can't wait to take the stage with musical giants Carole King and Roy Ayers for some ridiculously one-of-a-kind performances."
Ayers performed at the inaugural Black Ball in 2004 and soprano Battle sang alongside Keys at the 2007 event.
King was slated to perform at last year's (12) benefit, which was cancelled due to Hurricane Sandy.