Bayern are five-time European champions, while the Parisians have never won the continent's top honour.
Boosted by the huge deals they completed to sign Neymar and Kylian Mbappe this summer, however, Unai Emery's team will be looking to make a statement at Parc des Princes this week.
|Game||PSG vs Bayern Munich|
|Date||Wednesday, September 27|
|Time||19:45 BST / 14:45 ET|
TV CHANNEL & LIVE STREAM
In the UK, the match will be available to watch live on television on BT Sport Extra 2 and by stream via the BT Sport app.
|UK TV channel||Online stream|
|BT Sport Extra 2||BT Sport app|
In the US, the match will be available to watch live on television on Fox Soccer Plus and by stream via Fox Sports Go or WatchESPN.
|US TV channel||Online stream|
|Fox Soccer Plus||Fox Sports Go / WatchESPN|
SQUADS & TEAM NEWS
|Defenders||Silva, Kimpembe, Marquinhos, Meunier, Berchiche, Kurzawa, Alves|
|Midfielders||Verratti, Lucas, Motta, Di Maria, Lo Celso, Draxler, Nkunku, Rabiot|
|Forwards||Cavani, Neymar, Mbappe|
Angel Di Maria and Neymar are both available after recent absences.
Hatem Ben Arfa is out of favour and will not feature and while Javier Pastore is back in training, this match will come too soon for him to be included in the squad.
Potential starting XI: Areola; Alves, Marquinhos, Silva, Kurzawa; Verratti, Motta, Rabiot; Mbappe, Cavani, Neymar.
|Goalkeepers||Starke, Ulreich, Fruchtl|
|Defenders||Sule, Hummels, Martinez, Rafinha, Boateng, Rudy, Alaba|
|Midfielders||Thiago, Ribery, Robben, James, Vidal, Tolisso, Kimmich|
|Forwards||Lewandowski, Muller, Coman|
David Alaba is available again for Bayern after an ankle injury and Tom Starke has come out of retirement due to Manuel Neuer's injury.
Aside from Neuer, Juan Bernat is the only player Carlo Ancelotti will be missing in Paris.
Potential starting XI: Ulreich; Kimmich, Boateng, Hummels, Alaba; Thiago, Vidal; James, Muller, Ribery; Lewandowski.
BETTING & MATCH ODDS
PSG are evens favourites to win, according to dabblebet, with Bayern priced at 12/5 and the draw available at 11/4.
Both Carlo Ancelotti and Unai Emery have a reputation as European specialists.
During the 2013-14 season, in fact, these two coaches collected the continent's two top honours, with Ancelotti winning the Champions League with Real Madrid and Emery guiding Sevilla to the first of three consecutive Europa League triumphs.
Ancelotti has been a member of world football's elite coaching group for some time and Emery's work at Sevilla earned him a promotion to that club and the job at Paris Saint-Germain.
Both endured difficult first seasons at their respective clubs, however, with the Italian taking the reins at Bayern Munich.
Ancelotti at least won the league title that has become custom for Bayern, but Emery was pipped to it by a young, exciting Monaco team.
PSG's woes were compounded by their astonishing exit at the hands of Barcelona in the last 16 of the Champions League, while Bayern progressed only one round further before being beaten by Real Madrid.
This season, the pressure will be on both clubs to go further in the competition.
They will have the chance to measure themselves against another top side - each other - for the first time this campaign on Wednesday night.