Roma began the group phase with an away draw against Bayern, while Ajax secured an impressive 2-0 victory over Paris Saint-Germain.
Match preview
Roma are hoping to replicate last season's European success after they reached the quarter-finals in their first appearance in the Champions League group stage.
The Serie A champions cruised through a qualifying tie against Vorskla Poltava to advance to the main competition, where they have been drawn into a tough group featuring Ajax, Bayern Munich and Paris Saint-Germain.
They looked to be heading towards defeat in their opening group match against Bayern, conceding two first-half goals to leave themselves with a mountain to climb in the second period.
The Italian club ultimately rose to the challenge as Evelyne Viens pulled a goal back to give Roma foothold, before Manuela Giugliano scored a stoppage-time equaliser to ensure her side returned home with a precious point.
After going on to beat Sassuolo 2-0 in Sunday's league clash, Roma have now won 11 and drawn one of their 12 competitive matches this season, and they will be determined to extend their unbeaten run when they face Ajax in their first home game of the group stage.
Meanwhile, Ajax are making their first appearance in the group stage after negotiating qualifying ties against Dinamo-BGU and Zurich.
Despite being drawn in a tough group, Ajax showed no signs of nerves in their opening match against French giants PSG, which was played at the Johan Cruyff Arena in Amsterdam.
Tiny Hoekstra opened the scoring in the 34th minute, before Sherida Spitse kept her composure from the penalty spot to help the Dutch champions clinch a 2-0 victory.
After extending their unbeaten start to the season to 10 games, Ajax were brought quickly down to earth in Sunday's home league meeting with title rivals Twente, as they fell to a narrow 1-0 loss following Renate Jansen's first-half effort.
Although they would have been upset to see their fine run of form come to an end, Suzanne Bakker's side will head to Rome with confidence, having won 10 consecutive away games since losing to Twente in February.
Roma Women Women's Champions League form:
W
L
D
Roma Women form (all competitions):
Ajax Women Women's Champions League form:
Ajax Women form (all competitions):
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Team News
Roma boss Alessandro Spugna is set to bring goalkeeper Camelia Caesar back into the side after she dropped down to the bench on Sunday.
Lucia Di Guglielmo and Valentina Giacinti were rotated out of the side at the weekend, but the pair are expected to return for Thursday's home clash.
Despite having to settle for a substitute role against Bayern last week, Giada Greggi could feature in midfield alongside Giugliano and Saki Kumagai.
As for the visitors, Bakker is still unable to call upon long-term injury absentees Roos van der Veen and Nikita Tromp.
After being left on the bench at the weekend, 18-year-old defender Isa Kardinaal is expected to return for the trip to Rome.
Romee Leuchter will be one of Ajax's main goal threats, having scored 15 times in 12 competitive appearances this season.
Roma Women possible starting lineup:
Ceasar; Aigbogun, Minami, Linari, Di Guglielmo; Giugliano, Kumagai, Greggi; Viens, Haavi, Giacinti
Ajax Women possible starting lineup:
Van Eijk; Kardinaal, Spitse, De Sanders, Weerden; Noordam, Van Gool, Yohannes; Grant, Hoekstra, Leuchter