The world champion had booked his place in the evening match with a 4-3 win over Liang Wenbo in the afternoon. Brecel had dominate Judd Trump 4-0, with two centuries on the way to victory.
Selby, who beat Mark Allen 10-7 to clinch the International Championships final last week, nearly made an incredible comeback fighting back from 5-2 to 5-4 behind against the Belgian.
But Brecel, who won the China Championship in August, produced a stunning break to win the frame on the black.
The Champion of Champions is an invitational event contested between the winners of the season's major tournaments over the past year starting from world champion Selby's victory at the UK Championship last December.
Defending champion John Higgins begins his campaign on Thursday against fellow Scotsman Anthony McGill in a Group Four that also contains Ronnie O'Sullivan and Neil Robertson.
Champion of Champions results/schedule
Group Two results (Tuesday November 7)
- Marco Fu 3-4 Michael White
- Shaun Murphy 4-2 Mark King
- Final (best of 11 frames)
- Michael White 4-6 Shaun Murphy
Group One results (Monday November 8)
- Ding Junhui 2-4 Anthony Hamilton
- Barry Hawkins 2-4 Ryan Day
- Anthony Hamilton 6-4 Ryan Day
Group Three fixtures (Wednesday November 8)
- Mark Selby 4-3 Liang Wenbo
- Judd Trump 0-4 Luca Brecel
- Selby 4-6 Brecel
Group Four fixtures (Thursday November 9)
- Ronnie O'Sullivan v Neil Robertson
- John Higgins v Anthony McGill
- O'Sullivan/Robertson v Higgins/McGill
Semi-finals (best of 11 frames)
- Friday November 10
- Anthony Hamilton v Winner of Group Four
- Saturday November 11
- Shaun Murphy v Luca Brecel
- Final (best of 19 frames)
- Sunday November 12