O’Sullivan, who won the world title for a fifth time this year, will take on world number 13 Mark Davis in their opening group match in the inaugural competition, promoted by Matchroom Sport, in the Jaguar Exhibition Hall.
Leicester’s Mark Selby will pot his first ball on the green baize in Coventry against Shaun Murphy when the tournament gets underway on Tuesday, November 19, which will be followed by John Higgins when the Wizard of Wishaw plays Stephen Maguire.
The next day’s play sees world number four Judd Trump face Marco Fu before an all-English affair when Ricky Walden takes on Stuart Bingham.
Thursday’s action involves Australian Neil Robertson and Martin Gould ahead of the showdown between left-hander Mark Allen and Ali Carter, who has successfully returned to the game following treatment for testicular cancer.
O’Sullivan enters the group stages on Friday and his match against Davis will be followed by Ding Junhui’s equally-anticipated clash against Barry Hawkins.
O’Sullivan said: “I am looking forward to playing in the 888casino Champion of Champions competition being held at the Ricoh Arena Coventry. It is always exciting to play in a new tournament at a new venue.
“Everybody taking part in the 888casino Champion of Champions is a winner and it's nice that the winner gets £100,000. It should be a really good, competitive event and I am sure everyone will be bringing their A game to the table. “I have played in quite a few tournaments recently and am enjoying snooker although it can be frustrating at the best of times as I always feel I can do better.
“I am looking forward to the event getting underway and to start playing some of the top players in the world. It should be a good challenge.”