These two teams will be locking horns for the first time since the 2018 Champions League final, when the Spanish champions triumphed 3-1 courtesy of a second-half double from Gareth Bale.
Los Blancos will be looking to claim an advantage on home soil ahead of the second leg of their last-eight tie at Anfield on April 14.
Some of Europe's biggest talents will be on display here and with that in mind, Sports Mole picks a combined XI from both squads, using only players available for the contest.
The goalkeeping spot in this particular side was difficult to pick, with both teams having two world-class stoppers. Alisson Becker has not always been at his best for Liverpool this season, but the 28-year-old just about gets the nod between the sticks. Alisson has an impressive record in the Champions League this season, keeping four clean sheets in five appearances, while Madrid's Thibaut Courtois has kept just three clean sheets in eight outings, conceding 10 times in the process.
Dani Carvajal's absence through injury means that Trent Alexander-Arnold is selected at right-back, with the Englishman answering some of his critics against Arsenal on Saturday with a fine display. Meanwhile, Andrew Robertson just about gets the nod over Ferland Mendy on the left; the Frenchman has been in strong form for Los Blancos this season, but it is difficult to ignore Robertson's performances over the last couple of seasons.
Sergio Ramos would have been a certainty had he been available, and the same can also be said for Virgil van Dijk. Neither will feature on Tuesday through injury, though, and it is an easy decision to select Raphael Varane as one of the two central defenders. Fabinho has been back in midfield for Liverpool in recent matches, but the Brazilian has been shifted back to the defence for the purposes of this side as he simply had to be included.
Thiago Alcantara has been controversially left out of the midfield, but it would be fair to say that the Spaniard has struggled to find his best form since arriving at Anfield. Casemiro, though, has again been impressive for Madrid this term, and it is very difficult to leave out either Luka Modric or Toni Kroos considering the success that they have enjoyed, particularly in this competition. As a result, it is an all-Madrid midfield three, with Thiago just missing out despite his standing in European football.
The front three, in truth, was not difficult to choose. Sadio Mane has only scored 12 times and registered just seven assists in 38 appearances for Liverpool this season, but he remains a hugely important player for the Reds and is given the nod over Eden Hazard, who continues to struggle for minutes due to a series of injuries.
Mohamed Salah's future at Anfield continues to be called into question, but the Egypt international again showed his class against Arsenal on Saturday, and he has been in excellent form again this season, scoring 26 times in 41 appearances in all competitions, including five goals in eight Champions League outings.
The final position in the XI goes to Karim Benzema, who has scored 24 times in 33 appearances for Los Blancos this season, including five goals in six Champions League appearances. The 33-year-old's contract at the Bernabeu expires next summer, but he is still one of the leading forwards in European football, and it was not a difficult decision to choose him over the likes of Diogo Jota, Roberto Firmino and Vinicius Junior in this side.