While the hosts have qualified for the knockout rounds, Benfica have been eliminated after picking up six points from their five group games.
Match preview
Bayern Munich have fared well in their Champions League campaign up until this point, winning four and losing only one of their five matches in the main draw.
They demonstrated their fighting qualities to come from behind to win against Rosengard and Benfica, but they could do nothing to prevent Barcelona from cruising to a 3-0 win at Camp Nou.
However, Bayern recorded a statement 3-1 win in the reverse fixture to become the first team to beat Barcelona in any competition this term.
Last week, Alexander Straus's side secured their place in the quarter-finals with a commanding 4-0 victory over Rosengard thanks to goals from Tainara, Sydney Lohmann, Georgia Stanway and Julia Landenberger.
Bayern are level on points with the group leaders, but they are behind the Catalan giants due to the head-to-head record between the two sides, and they will only be able to finish in top spot if they can better Barcelona's result.
Meanwhile, Benfica will want to finish their European campaign on a positive note despite failing to qualify for the knockout rounds.
Benfica showed great character to remain competitive in the group stage after being thrashed 9-0 by Barcelona in their opening game of the main draw.
They then gave up a two-goal lead to lose 3-2 to Bayern Munich, before they bounced back with two victories over Rosengard.
However, any hopes of reaching the quarter-finals dissipated last week when Benfica were beaten 6-2 by Barcelona, in a game where Filipa Patao's side missed two penalties.
Although Wednesday's contest represents their final match of the 2022-23 Champions League, Benfica will be determined to claim a seventh consecutive away win in all competitions.
Bayern Munich Women Women's Champions League form:
Bayern Munich Women form (all competitions):
Benfica Women Women's Champions League form:
Benfica Women (all competitions) form:
Team News
Bayern are still without the services of Jovana Damnjanovic, Hanna Glas and Giulia Gwinn due to injury issues.
With Linda Dallman and Maximiliane Rall also unavailable, Straus is expected to name an unchanged lineup following Bayern's comfortable win over Rosengard last week.
Lea Schuller has scored 10 goals in all competitions this season, and the 25-year-old will be looking to add to her tally when she leads the line on Wednesday.
As for the visitors, Ana Seica will partner Carole Costa in the centre of defence, while Valeria and Catarina Amado are expected to operate as the two full-backs.
Nycole Raysla lost her place in the starting lineup for the 6-2 defeat to Barcelona, but she is expected to be included in the starting lineup against Bayern.
Including qualifying, Cloe Lacasse has scored seven goals in nine Champions League appearances this season, and she will be aiming to continue her impressive form in Benfica's final group game.
Bayern Munich Women possible starting lineup:
Grohs; Tainara, Viggosdottir, Kumagai, Simon; Magull, Stanway, Zadrazil; Lohmann, Buhl, Schuller
Benfica Women possible starting lineup:
R. Costa; Valeria, Seica, C. Costa, Amado; Pauleta, Nazareth, Ucheibe; Vitoria, Lacasse, Raysla