Button, who has competed in the ROC on four previous occasions, will compete in the main event and also team up with endurance sportscar racer Alex Buncombe to represent Great Britain in the ROC Nations Cup - in which he finished runner-up in 2009.
"I can't wait to be back at the Race of Champions again - and especially to be racing at home at London's former Olympic Stadium,” said the McLaren driver.
"It is always a very special event with a good atmosphere. You're racing against guys from your own series, plus others from all over the world.
"We get to meet friends old and new from the different forms of motorsport so we enjoy our time both on and off the track.
"It's always a lot of fun, but everyone wants to put on a good show for the fans - and of course we only pretend to be taking it easy before giving it everything when we're sitting in the car on the line.
"I look forward to partnering Alex Buncombe in the RoC Nations Cup too.
"Germany had an annoying habit of beating us at Wembley in 2007 and 2008, so it's about time we made it all the way now we'll be racing on the other side of London."
Button is the seventh F1 driver to sign up for this year's event: Romain Grosjean, Felipe Massa, Daniel Ricciardo, Susie Wolff, Sebastian Vettel and Nico Hulkenberg will also be competing, with the latter duo representing Team Germany in the popular Nations Cup format.
The Race of Champions takes place at London's Queen Elizabeth Olympic Park on November 20-21.