With three final appearances between the sides, they will both be hoping this is the season they can win their first European trophy.
Match preview
While PSG have been runners-up on three occasions, they have failed to make it past the semi-final stage for the last three seasons.
As a result of finishing second in Division 1 Feminine last term, PSG had to negotiate a qualifying round tie to progress to the group stage.
The French side cruised to a 4-1 aggregate victory over Hacken to secure their place in a group that features Chelsea, Real Madrid and Vllaznia.
PSG will head into Tuesday's contest in a confident mood after embarking on a seven-game unbeaten run since losing to Lyon in the Trophees des Championnes.
The hosts have also been in impressive form at home this season, winning all four competitive games by a 9-3 scoreline.
Meanwhile, Chelsea will be aiming to win the competition for the first time in their history after losing to Barcelona in the 2020-21 final.
The Blues failed to match their memorable run to the final in last season's Champions League campaign when they were unable to progress from the group stage.
Chelsea were drawn into a group that contained Wolfsburg and Juventus last term, and their task will not get any easier this time around.
After leading the team to a 3-1 victory over Everton on Sunday, Denise Reddy will continue to take charge of on-field matters in the absence of Emma Hayes, who is recovering from an emergency hysterectomy.
The Blues will travel to Paris off the back of three consecutive victories where they have scored at least two goals in each game.
Paris Saint-Germain Women form (all competitions):
W
W
W
D
L
L
Chelsea Women form (all competitions):
W
W
L
W
W
W
Team News
Former Lyon goalkeeper Sarah Bouhaddi will be shielded by the centre-back pairing of Amanda Ilestedt and Elisa De Almeida.
After coming off the bench at half time against Dijon on Saturday, Kadidiatou Diani is expected to return to the starting lineup for Thursday's contest.
Ramona Bachmann will also be brought into the side to lead the line, and the forward will be aiming to score in a third consecutive game for PSG.
As for the visitors, Jelena Cankovic is a doubt after the midfielder missing the win over Everton with a slight knock.
Pernille Harder returned from injury to score a brace in Sunday's victory, and the Denmark international will retain her place in the side.
Fran Kirby was unavailable at the weekend through illness, but the England international could be fit enough to start against PSG.
Paris Saint-Germain Women possible starting lineup:
Bouhaddi; Lawrence, De Almeida, Ilestedt, Karchaoui; Groenen, Jean-Francois, Geyoro; Martens, Diani, Bachmann
Chelsea Women possible starting lineup:
Berger; Bright, Buchanan, Eriksson; Perisset, Cuthbert, Fleming, Reiten; Kirby, Harder, Kerr