Both sides kicked off their domestic campaigns with victories at the weekend and will face off to meet either Rangers or Union SG for a spot in the group stage.
Match preview
Despite putting five goals past Ajax in a frenetic Super Cup encounter - which seemed to sap PSV's energy - Ruud van Nistelrooy's side experienced far less joy on the attacking front during their trip to the Stade Louis II, playing out a 1-1 first-leg tie with Monaco.
The KNVB-Beker holders did go into half time with a 1-0 lead thanks to Joey Veerman's opener, but Axel Disasi's equaliser 10 minutes from time means that it is all to play for in the Netherlands this week.
Commencing yet another quest to end Ajax's perennial reign of dominance in the Eredivisie, PSV will enter the second leg off the back of a straightforward 4-1 opening-day success over Emmen, during which the much-coveted Cody Gakpo bagged a brace.
Speculation surrounding Gakpo's future is not letting up amid links with a switch to either Manchester United or Arsenal, but Van Nistelrooy is not prepared to lose the prolific attacker before PSV's European fate is sealed, as they aim to return to the group stage for the first time since 2018-19.
The consolation prize of a spot in the Europa League group stage will be theirs if they fail to get the better of Monaco this week, and the fact that his side have shipped five goals in their opening three matches may be a point of concern for Van Nistelrooy.
A Strasbourg side only heading in one direction up the Ligue 1 status ladder would have hoped to take advantage of Monaco's jellied legs at the weekend, but Les Monegasques still found a way to grind out a hard-fought success in their domestic opener.
Krepin Diatta and Sofiane Diop found the back of the net before Habib Diallo made things interesting 25 minutes from time, but it was Monaco who looked more likely to score again, with Matz Sels forced to make as many as nine saves in the Strasbourg goal.
Scoring just two goals from 24 shots at the Stade de la Meinau would have irked Philippe Clement a tad - especially seeing as his side had 15 shots in the first leg with PSV and only found the back of the net once - but three points on the opening day is of paramount importance nonetheless.
Monaco navigated their way to the Champions League qualifying playoff round last year before bowing out at the hands of Shakhtar Donetsk, and as is the case with PSV, Les Monegasques are also aiming to return to the promised land for the first time in four seasons.
With the visitors' unbeaten run away from home in all competitions now standing at seven games, Clement's side will hope to continue their European journey at the expense of PSV's, although they did lose their most recent continental game away from home against Braga in the Europa League last-16 stage.
PSV Eindhoven Champions League form:
PSV Eindhoven form (all competitions):
Monaco Champions League form:
Monaco form (all competitions):
Team News
PSV did not pick up any fresh concerns in their Eredivisie success over Emmen, but their treatment room is still well-occupied, with Carlos Vinicius, Noni Madueke, Mauro Junior and Olivier Boscagli all absent at the weekend.
Johan Bakayoko did not earn any minutes in the first leg but has put himself in contention for a start here with a goal at the weekend, as Gakpo and Luuk de Jong also prepare to hold the fort up top.
Ibrahim Sangare and Guus Til were both rested at the weekend with the second leg in mind, and Van Nistelrooy could also afford to bring Philipp Max and Joey Veerman off early against Emmen with his side 3-0 up at half time.
As for Monaco, Aleksandr Golovin and Kevin Volland will both make timely returns to the squad after serving suspensions in the win over Strasbourg, but Diop and Diatta will not cede their places easily after scoring at the weekend.
Caio Henrique remains a doubt after testing positive for COVID-19, and the likes of Benoit Badiashile, Myron Boadu, Willem Geubbels and new signing Takumi Minamino are all sidelined by injury too.
Breel Embolo was chosen to lead the line at the weekend, but Wissam Ben Yedder will certainly come back into the fold here, while Vanderson and Eliot Matazo can also expect to return to the first XI.
PSV Eindhoven possible starting lineup:
Benitez; Hoever, Teze, Obispo, Max; Sangare, Veerman, Til; Bakayoko, De Jong, Gakpo
Monaco possible starting lineup:
Nubel; Vanderson, Disasi, Maripan, Jakobs; Matazo, Fofana; Diop, Volland, Golovin; Ben Yedder
We say: PSV Eindhoven 1-2 Monaco (Monaco win 3-2 on aggregate)
Both managers could afford to rest key names at the weekend, but both must also work around a number of injury concerns for the second leg, which should prove to be another tense and closely-fought affair.