The Blues currently have the upper hand after they produced a strong away performance to claim a 1-0 win at Estadi Olimpic Lluis Companys last weekend.
Match preview
Chelsea will carry a narrow lead into Saturday's second leg after they condemned Barcelona to their first competitive home defeat since February 2019.
Erin Cuthbert fired Chelsea in front in the 40th minute, before the Blues produced a stubborn defensive display to become the first team to stop Barcelona from scoring since Wolfsburg in April 2022.
The reigning Women's Super League champions have had a full week to reflect upon the first leg and prepare for Saturday's return fixture, as they look to protect their lead and reach their second Champions League final.
Chelsea, who are hoping to win their first European trophy, will look to continue their impressive home form, having lost just one of their previous 22 competitive home matches.
The Blues have lost only one fo their home games in their four previous semi-final appearances, but that 1-0 defeat did take place against Barcelona last season.
Unlike their hosts, Barcelona were in league action in midweek, as a much-changed team fought back from behind to beat Levante Las Planas.
A Claudia Pina brace as well as goals from Marta Torrejon and Bruna Vilamala secured a 4-2 away win, ensuring Barcelona are still yet to lose a league game this season.
While they are on the brink of retaining their league title, the Catalan giants have work to do if they are to defend their Champions League trophy in next month's final at San Mames.
Barcelona will look to draw upon their recent European experience, having progressed from each of their last three Champions League semi-finals since losing a one-legged tie to Wolfsburg in 2019-20.
Jonathan Giraldez's side have won 17 of their 18 competitive away games this season, scoring three goals or more in 13 of their previous 15 road trips.
Chelsea Women Women's Champions League form:
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D
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Chelsea Women form (all competitions):
Barcelona Women Women's Champions League form:
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L
Barcelona Women form (all competitions):
Team News
Chelsea boss Emma Hayes is unable to call upon Maren Mjelde, Nathalie Bjorn, Aniek Nouwen, Sam Kerr and Mia Fishel.
Club captain Millie Bright is likely to be on the bench after she returned from a lengthy spell on the sidelines to be an unused substitute for the first-leg win over Barcelona.
After seeing her side produce a strong performance last week, Hayes could decide to select an unchanged lineup for the return leg at Stamford Bridge.
As for the visitors, they remain without the services of defender Mapi Leon, who has been sidelined since December with a knee injury.
After making wholesale changes in midweek, Giraldez is expected to name a similar side to the one that started the first leg.
However, Pina could be one of the players to retain her spot after scoring a brace in Wednesday's win over Levante Las Planas.
Chelsea Women possible starting lineup:
Hampton; Carter, Buchanan, Charles; Rytting Kaneryd, Cuthbert, Leupolz, Nusken, Lawrence; James, Ramirez
Barcelona Women possible starting lineup:
Coll; Batlle, Paredes, Engen, Rolfo; Bonmati, Walsh, Guijarro; Graham Hansen, Pina, Paralluelo