Emma Hayes's side bypassed the qualifying rounds thanks to their Women's Super League triumph last term and now set out on a mission for a maiden continental triumph, having finished as runners-up to Barcelona in the 2020-21 season.
The Blues will now reunite with Real Madrid only a year on from doing battle with the Spanish giants in the 2022-23 group stage, where they won 2-0 at Kingsmeadow before being held to a 1-1 draw at the Estadio Alfredo Di Stefano.
Also joining Chelsea and Real Madrid - who reached the 2021-22 quarter-finals - in Group D are French outfit Paris Women, who defeated Arsenal in the qualifying rounds en route to a first group-stage appearance since progressing to the 2012-13 semi-finals.
Swedish Damallsvenskan leaders BK Hacken complete the section, while defending champions Barcelona Women will take on four-time winners Eintracht Frankfurt Women, Rosengard and Benfica Women.
Paris Saint-Germain Women - who defeated Manchester United 4-2 on aggregate in a two-legged qualifying tie - have been drawn to face Bayern Munich Women, Roma Women and Ajax Women in a tantalising Group C, while eight-time winners Lyon Women are up against Brann Women, Slavia Prague Women and St Polten Women in Group B.
WOMEN'S CHAMPIONS LEAGUE GROUP STAGE DRAW IN FULL
Group A: Barcelona, Rosengard, Benfica, Eintracht Frankfurt
Group B: Lyon, Slavia Prague, St Polten, SK Brann
Group C: Bayern Munich, PSG, Roma, Ajax
Group D: Chelsea, Real Madrid, BK Hacken, Paris FC