Audley Harrison will return to the ring in the Prizefighter competition at York Hall, Bethnal Green, on 23 February.
Former Commonwealth champion Martin Rogan, 41, will also compete in the eight-man knockout tournament.
Great Britain's Olympic boxing captain Tom Stalker will make his professional debut on the undercard.
Prizefighter is an eight-man competition where each fight lasts three rounds, with the quarter-finals, semi-finals and final all taking place on the same evening.
Heavyweights Harrison and Northern Irishman Rogan are former winners of previous Prizefighter events, with Harrison winning a tournament in 2009 before going on to win the European heavyweight title against Michael Sprott six months later.
That set up Harrison with a world title shot against David Haye in November 2010, but he was outclassed against his fellow Briton and was stopped in the third round.
Harrison then had to dismiss suggestions he should quit after a disastrous first-round knockout against David Price in Liverpool in October 2012, saying on Twitter: "One more shot at glory. It could be over; next fight will tell me. See you in a ring real soon."
Rogan, who won the Commonwealth belt when he beat Matt Skelton in February 2009, will be competing in his first fight since suffering a fifth round defeat against Tyson Fury in April.
American Travis Walker, 33, who has a win-loss record of 39-8, will also compete in Prizefighter, as will 31-year-old Briton Ian Lewison, who has made a promising start to his career - winning six and drawing once in his opening eight bouts.
Light-welterweight Stalker, who was controversially beaten in the quarter-finals at the London Games, turned professional on Wednesday and will make his debut in front of the television cameras.
He is then scheduled to fight in his native Liverpool on the undercard of Tony Bellew's clash against Isaac Chilemba on 30 March.