The performance, part of a BBC live broadcast, will be the first time the group has performed together in 15 years.
Culture Club, fronted by Boy George, will be joined by an array of big names for the concert on Saturday July 19.
The performers include Kaiser Chiefs, Smokey Robinson, Rizzle Kicks, Paloma Faith, Katherine Jenkins, Il Divo, One Republic, Taio Cruz, Alfie Boe and Pumeza.
Bill Bailey will also bring his unique brand of musical humour to the evening, with the BBC Scottish Symphony Orchestra and Fred MacAulay making special guest appearances.
Executive producer Guy Freeman says: "Having Culture Club perform for the first time in 15 years is fantastic in its own right, but for them to be part of an already amazing line-up will make this a very special night."