This is a repeat of the 2018 round-of-16 tie, when the Spanish side eased comfortably through on aggregate following a 2-1 second leg win in Paris.
PSG have been eliminated at the first time of asking in the knockout stages in each of the last three seasons, while Zinedine Zidane's squad fell well short of adding to the club's 13 titles last season, crashing out against Ajax.
With Galatasaray and Club Brugge making up the rest of the group, both sides will be confident of progressing irrespective of the result in their first test.
Here, Sports Mole has selected its strongest combined XI from the two squads, using only players available on Wednesday.
PSG keeper Keylor Navas moved to the Parc des Princes from Madrid in the summer, and while the Costa Rica regular would be an excellent choice between the sticks, the pedigree of Thibaut Courtois, the Belgium and former Chelsea shot-stopper he left behind, would probably prevail were most critics given the choice.
The hosts also have ample quality in defence, including 34-year-old Brazil favourite Thiago Silva at centre-back, but Madrid's redoubtable contingent makes up three-quarters of the backline.
Among a series of absentees for their trip to Paris, Madrid's freshest concern is left-back Marcelo, whose neck injury would provide an opportunity in a combined XI for Layvin Kurzawa, who has the distinction of being the first defender in the modern-day Champions League to have scored a hat-trick in the competition.
That means PSG pair Pablo Sarabia and Angel Di Maria have the creative freedom to push forward, although it would be remiss not to mention that Eden Hazard and Luka Modric would take their places were they not missing through injury for this match.
Injuries also shape the look of the attack, which is missing Neymar through suspension for a number of unwise comments about the standard of refereeing, as well as the rehabilitating Kylian Mbappe and Edinson Cavani.
With 60 Champions League goals in his career so far, Karim Benzema is the fourth-highest all-time scorer in the competition, ahead of the likes of Ruud van Nistelrooy, Thierry Henry and Zlatan Ibrahimovic.
Eric Maxim Choupo-Moting is a somewhat less experienced forward and is yet to score in Europe for PSG, but the former Stoke City striker has scored three times in two appearances this season while Neymar has been out of action.