The 'Faith' singer will appear at the ball at London's Roundhouse on June 15, alongside previously-confirmed hosts Alicia Keys and Mark Ronson, as well as further musical performances from Paloma Faith and Tinie Tempah.
"I've been a fan of George Michael for as long I can remember. He is a legend and an inspiration. His work raising awareness and funds for those suffering with the HIV virus has spanned three decades," commented Keys in a statement.
"I'm honoured that George has lent his voice to our KCA cause and I'm so excited that he's singing for us at the Black Ball in London. It's going to be an amazing night!"
All proceeds made on the night will contribute to help combat HIV and AIDS victims in Africa and India.
Michael recently announced details for a European tour called 'Symphonica', which will see the star rework a selection of tracks from his back catalogue for an orchestra.