Meanwhile, Real Madrid have already been in European action this season, having successfully negotiated a qualifying tie against Sporting Lisbon.
Match preview
Chelsea are on four teams that will begin their European campaign in the group stage after they secured automatic qualification via their successful Women's Super League title defence.
The Blues edged out Manchester City on goal difference to clinch their fifth consecutive title and seal their spot in the final UWCL group stage before the format moves to a league phase for next season.
Chelsea are looking forward to playing their first European game under Sonia Bompastor, who previously won the competition with French giants Lyon in 2021-22.
Bompastor has made a promising start to her tenure as Chelsea boss, having seen her side edge out Aston Villa and thrash Crystal Palace via a 7-0 scoreline.
Chelsea have not played since sweeping past the Eagles after Sunday's clash with Manchester United was postponed due to the short distance between that scheduled meeting and Tuesday's home game against Real Madrid.
The Blues are preparing to face the Spanish side in the group phase for the third consecutive season, and they will take great confidence from the fact they have won two and drawn two of their four head-to-head meetings.
Real Madrid are set to appear in their fourth consecutive UWCL group stage after they successfully negotiated a second-round qualifying tie against Sporting.
Athenea del Castillo and Melanie Leupolz got on the scoresheet to fire Real Madrid to a 2-1 win in the away leg, before they came from behind to record a 3-1 victory in the return leg thanks to a Sandie Toletti brace and an Alba Redondo effort.
Las Blancas will be desperate to enjoy a successful European campaign after they mustered just one point in last season's group stage exit.
They will certainly travel to the English capital in a positive mood, recording seven consecutive victories this season, including a narrow win in Friday's home clash with Valencia.
Olga Carmona's first-half effort proved enough to fire Real Madrid to a 1-0 victory, ensuring they remain level on points with rivals Barcelona and Atletico Madrid in Liga F.
While they boast a 100% record in 2024-25, Real Madrid have struggled in recent away trips in the UWCL main draw, having lost five of their previous six away group games.
Chelsea Women form (all competitions):
L
W
W
W
W
W
Real Madrid Femenino Women's Champions League form:
W
W
Real Madrid Femenino form (all competitions):
Team News
Chelsea remain without the services of Sam Kerr, Mia Fishel, Sophie Ingle, Aniek Nouwen, Niamh Charles and Oriane Jean-Francois.
Colombia international Mayra Ramirez could return to the side after dropping down to the bench against Palace.
Kadiesha Buchanan may also be considered for the recall, with the 28-year-old hoping to get the nod over Nathalie Bjorn as Millie Bright's central defensive partner.
As for the visitors, Toletti will have to be assessed after she was forced off in the first half against Valencia.
After making changes on Friday, Real Madrid boss Alberto Toril is set to recall Maelle Lakrar, Teresa Abelleira and Eva Navarro.
Leupolz is set to line up against her former club after leaving Chelsea for the Spanish capital in the summer transfer window.
Chelsea Women possible starting lineup:
Hampton; Bronze, Buchanan, Bright, Lawrence; Cuthbert, Nusken; Rytting Kaneryd, James, Reiten; Ramirez
Real Madrid Femenino possible starting lineup:
Misa; Hernandez, Lakrar, Mendez, Carmona; Leupolz, Abelleira; Navarro, Moller, Caicedo; Redondo