The two stars will help celebrate the 50th anniversary of human rights group Amnesty International at the fundraising comedy show on Sunday, March 4 in New York City.
Saturday Night Live's Taran Killam, Jay Pharoah and Bobby Moynihan will also perform during the Secret Policeman's Ball as will British comics Jimmy Carr and Matt Berry.
Rex Lee and Tim Roth join the list of celebrity presenters for the Radio City Music Hall event.
Russell Brand, Jon Stewart, Sarah Silverman, Kristen Wiig and The Muppets were all previously confirmed to be taking part in the Secret Policeman's Ball.
Seth Meyers, Bob Odenkirk, David Cross and Noel Fielding are also on the bill.
Coldplay and Mumford & Sons will be on to hand to perform cuts from their most recent albums.
John Cleese and producer Martin Lewis first organised a series of Secret Policeman's Balls in the 1970s and 1980s, which saw the members of Monty Python, Peter Cook, Billy Connolly and Rowan Atkinson sharing the stage in the UK.
The Secret Policeman's Ball will be broadcast on Friday, March 9 at 10pm on Channel 4 in the UK and will also stream live on EpixHD.com.
Watch John Cleese and Michael Palin perform Monty Python's 'Parrot Sketch' at The Secret Policeman's Ball below: