The Ligue 1 side ran out 3-0 winners in the reverse match earlier this season, although Madrid lead the head-to-head record four victories to PSG's three.
Los Blancos have also won the last two meetings between the two teams at the Bernabeu, with PSG's last away success in this fixture coming in the quarter-finals of the UEFA Cup Winners' Cup in 1994.
Some of the world's top players will be on display in the Spanish capital on Tuesday night.
With that in mind, Sports Mole has selected the best team from both squads, using only players available for the European clash.
The goalkeeping situation is an interesting one when considering that Keylor Navas effectively joined PSG over the summer having lost his spot at Madrid to Thibaut Courtois. There was an argument in Spain that Navas was the better of the two goalkeepers, and the Costa Rica international gets the nod between the sticks as Courtois has struggled to show his best form since arriving from Chelsea.
It would be fair to say that both of these teams are stronger in attack than in defence, meaning that we have selected a back three in a 3-4-3 formation, with none of the full-backs making it into the XI. Sergio Ramos divides opinion but the Spaniard is a born winner, whilst he has contributed four goals in 16 appearances for Los Blancos this season, including two in three Champions League outings.
Ramos is joined by Madrid teammate Raphael Varane, whose own form has also been the subject of scrutiny over the last 12 months or so. There is not a team in world football who would not want the 2018 World Cup winner, though, and he sails into this XI. The other spot at the back goes to Thiago Silva, who remains one of the best central defenders in world football at the age of 35.
The nature of this 3-4-3 formation means that the two wide midfielders had to be comfortable in that area of the field, and that is the case for both Angel Di Maria and Eden Hazard. Di Maria has nine goals and nine assists in 19 outings this season, including two goals and four assists in four Champions League appearances. Hazard has actually struggled to show his best form since arriving from Chelsea, but there is no question that the Belgian is one of the world's top players when in full flow.
As for two central midfielders, Luka Modric's form has been questioned this season, but the 2018 World Cup finalist has still managed two goals and five assists in 10 appearances in all competitions. Marco Verratti is still a slight injury doubt for Tuesday's match, although the Italy international is said to be winning his battle against a knee problem, and it is difficult to leave the 27-year-old out considering his talent.
There is not really another outstanding candidate to fill the spot from PSG, while neither Casemiro nor Toni Kroos deserve a spot in the XI ahead of Verratti or Modric, who would form quite the partnership.
Further forward is where it gets incredibly interesting considering that Mauro Icardi has scored 10 times in 11 appearances for PSG this season, while no player in the French club's history has found the back of the net on more occasions than Edinson Cavani. Madrid's Karim Benzema just takes the spot, though, having continued his fine form from last season in the opening months of this campaign.
The 31-year-old has managed 12 goals in 16 appearances in all competitions this term and would be the perfect player to operate alongside Kylian Mbappe and Neymar in attack. Mbappe is an absolute certainty having scored a staggering 69 goals in 99 appearances since joining PSG from Monaco.
Madrid can offer up the likes of Gareth Bale and Rodrygo Goes to fill the final spot in the XI, but Neymar just has to be in the team. Much has been made of the Brazilian's off-the-field conduct over the last 12 months; he has managed four goals in six appearances this season despite his injury troubles, though, and there is little doubting that he is one of the world's top players when his mind is entirely focused.