These two teams have met on six previous occasions in European football, and both have managed two wins.
The pair last clashed during the group stage of the 2015-16 competition; Real Madrid won 1-0 at the Bernabeu following a goalless draw in Paris.
Stay tuned for live minute-by-minute coverage of the action.
REAL MADRID: Navas; Nacho, Varane, Ramos, Marcelo; Kroos, Casemiro, Modric; Isco, Benzema, Ronaldo
PSG: Areola; Alves, Marquinhos, Kimpembe, Yuri; Verratti, Lo Celso, Rabiot; Neymar, Cavani, Mbappe
The referee brings the second period to a close with Real Madrid recording a 3-1 win overt PSG in the first leg of their last-16 tie. What an incredible game of football in the Spanish capital. Thanks for joining our live coverage of the match!
90 min+4 FULL-TIME: Real Madrid 3-1 PSG
90 min+3 Real Madrid have the ball as we enter the final stages of this match. The home side are going to win 3-1, which leaves things delicately poised ahead of the return fixture in Paris.
90 min+2 We are into the second of three additional minutes at the end of the match here.
90 min+1 BOOKING! Meunier (PSG) is booked for a foul on Asensio.
90 min Areola manages to keep out a curling effort from Ronaldo.
89 min SAVE! Navas is down to keep out a close-range effort from Mbappe!
87 min And Real Madrid have a third! Incredible scenes in Madrid as Marcelo gets his name on the scoresheet. The left-back managed to turn a low Asensio cross past Areola from inside the box!
86 min GOAL! Real Madrid 3-1 PSG (Marcelo)
86 min PSG SUB! Draxler replaces Lo Celso for the away side.
84 min Oh my word! Real Madrid score their second of the match in the 83rd minute as Ronaldo bundles the ball into the back of the net following a cross from Asensio! Areola palmed the ball back into the box, and it just hit Ronaldo before ending up in the goal!
83 min GOAL! Real Madrid 2-1 PSG (Ronaldo)
83 min Little over five minutes of the second period remaining, and PSG have just had a little spell with the ball. There has not been too much possession football tonight. More attack after attack!
81 min SAVE! Areola does well to keep out a poked effort from Bale.
81 min Real Madrid have an awful lot of attacking players on the pitch at the moment.
79 min REAL MADRID SUBS! Lucas and Asensio replace Casemiro and Isco.
79 min BOOKING! Nacho (Real Madrid) is booked for a foul on Neymar.
79 min Bale heads down towards Ronaldo inside the PSG box, but Marquinhos manages to make the clearance. This has been an incredible game of football, and the tempo is still just as high as it was in the first minute. How on earth is the score still 1-1? Lucas is about to enter for the home side.
77 min CHANCE! Alves just fails to make contact on a low cross from Berchiche as PSG continued to threaten the Real Madrid goal! The home side are really struggling at the moment.
76 min PSG are the better side at the moment as Real Madrid continue to lose the ball. There is no shape about the home team at the moment. Just Bale and Ronaldo stuck in the final third of the field.
74 min CHANCE! PSG centre-back Kimpembe sees his goal-bound effort blocked by Marcelo!
73 min Neymar releases Alves inside the Real Madrid box, but the right-back moves just too wide, and his cross is headed clear by Ramos. Off go Real Madrid down the other end of the field.
71 min Obviously an accident from Neymar, but the referee took a blow in the ear. His earpiece actually fell out, but all is well. Play resumes, and we still have more than 20 minutes of football to play here.
70 min Neymar has just smashed the ball at the referee, who holds his ear! Bizarre moment!
69 min REAL MADRID SUB! Bale replaces Benzema for the home side.
69 min Lo Celso sees his low effort move wide of the Real Madrid post.
68 min Bale is going to come off the Real Madrid bench in the next few minutes. Isco to leave the field? PSG have made a defensive change, but that will release Neymar into a central position.
66 min PSG SUB! Meunier replaces Cavani for the away side.
65 min... Ronaldo's free kick strikes the wall before dropping behind.
65 min The tempo of this match is just incredible. Hardly time to draw breath, and that has been the case since play resumed in the second period. Real Madrid are about to take their free kick...
64 min BOOKING! Rabiot (PSG) is booked for a poor challenge on Modric.
62 min CHANCE! Isco delivers a dangerous low cross into Benzema, but Areola does well to make the claim. Neymar is then chopped to the ground by Casemiro on the counter-attack.
61 min We are entering the stage of the match where both managers will be considering changes. There is some serious talent on both benches tonight. Bale could yet decide this match for Real Madrid.
59 min Little over 30 minutes of football remaining, and the tempo of the match has not dropped. Both teams are trying to work the ball in the final third of the field, and both defences are wobbling. You do get the feeling that there is another goal in this first leg, but for who? Stay tuned!
57 min Half-chance for Real Madrid this time as Ronaldo breaks into the PSG box, but the away side manage to scramble the ball behind. The resulting corner is then headed clear by Marquinhos.
55 min CHANCE! Rabiot's goal-bound strike is blocked by Ramos as Real Madrid wobble at the back. PSG have gone up a gear in the last few minutes. Brilliant stuff again.
54 min Mbappe races down the right before finding Alves, who swings a very dangerous cross into the Real Madrid box. Varane, however, just about does enough to make the clearance here.
52 min This is a super game of football. Absolutely brilliant. End-to-end action in Madrid.
50 min CHANCE! Super chance for the away side as Neymar finds Mbappe inside the Real Madrid box, but the Frenchman cannot find a route past Navas, who makes a smart save!
49 min Real Madrid have been the livelier of the two teams in the early stages of the second period. Ronaldo has a half-chance when Isco delivers into the box, but Marquinhos does well to block.
47 min... no changes from either side at the break, which is not much of a surprise. However, I suspect that both managers will have alterations in mind as the second period develops in Madrid.
46 min RESTART! Real Madrid resume the action here..
The referee brings the first period to a close with the two teams level at 1-1. Rabiot sent PSG ahead with a clever finish in the 33rd minute, but the home side levelled in the final stages of the first half when Ronaldo stuck his penalty into the bottom corner of the net.
45 min+2 HALF-TIME: Real Madrid 1-1 PSG
45 min+1 We are into the first of two additional minutes at the end of the first period.
45 min It looked like Ronaldo might have double touched that penalty, but nothing was given!
45 min Of course he scores! Ronaldo finds the bottom corner with a super penalty to score his 100th Champions League goal for Real Madrid! Big moment in this last-16 first leg!
45 min GOAL! Real Madrid 1-1 PSG (Ronaldo)
44 min Real Madrid have a penalty as Lo Celso pulls Kroos to the ground inside the box!
44 min PENALTY REAL MADRID!
42 min Dangerous moment inside the PSG box as Nacho's strike is not cleared and the ball stays in and around the penalty area, but the away side just about survive. Real Madrid have not had the luck thus far. The resulting corner is then headed clear by the excellent Kimpembe.
39 min CLOSE! Cavani has one deflected just wide of the Real Madrid post as the visitors threaten once again. Real Madrid's defence has been all over the place tonight.
38 min Half-chance for Real Madrid as Ronaldo finds a pocket of space in the final third, but he fires over the PSG crossbar. It is the away supporters that can be heard inside the Bernabeu at the moment.
36 min PSG are not happy as Kroos chops Mbappe to the deck, and both sets of players have their handbags out. Real Madrid need to be very careful as the away side continued to press here.
34 min Breakthrough! PSG take the lead in the 33rd minute as Rabiot finds the back of the net with a smart finish after the ball had fallen for the Frenchman inside the Real Madrid box!
33 min GOAL! Real Madrid 0-1 PSG (Rabiot)
33 min BOOKING! Isco (Real Madrid) is booked for a foul on Lo Celso.
31 min Neymar strikes into the arms of Keylor Navas following a mazy run in the final third.
30 min That Ronaldo chance came following a slip from Neymar, who has been all over the place in the opening 30 minutes. The Brazilian has been booked, and cannot seem to stay on his feet here.
28 min SAVE! Super save from Alphonse Areola as the PSG goalkeeper keeps out a strike from Ronaldo, who had been released by Marcelo. The ball seemed to hit Areola in the face!
26 min... CLOSE! Ronaldo misses the crossbar with his free kick.
25 min BOOKING! Lo Celso (PSG) is booked for a poor challenge on Isco, and Real Madrid have a free kick in a very dangerous position outside the away side's penalty box...
23 min Quite a scrappy period of the match in the last couple of minutes as the referee is forced to intervene following some late challenges. Neymar is getting a bit frustrated in a wide area, and the Brazilian needs to be careful having already been booked. Modric is the latest player to be chopped by Lo Celso.
21 min Isco delivers a dangerous cross into the PSG box, but Alves is on hand to make the clearance. Isco has been threatening for Real Madrid, but we have seen little from Benzema thus far tonight.
18 min There have been some very tasty challenges in the opening 18 minutes of this match. Neymar is on a yellow card, and I suspect Real Madrid's players will be looking to wind the Brazilian up here. PSG continue to grow into the contest as they enjoy more and more of the ball in the final third.
15 min BOOKING! Neymar (PSG) is booked for a late challenge on Nacho.
15 min Still goalless, but it has been a very bright 15 minutes of football here. Real Madrid were the better team in the early moments, although PSG are now seeing more of the ball in the final third. Neymar has just swept wide from close range, but the Brazilian was in an offside position.
13 min Another really dangerous moment for the home side as Neymar breaks down the left before delivering a low into Cavani, but Varane just about does enough. Nacho has been off-colour so far.
11 min Marcelo seems okay to continue, quite a quick recovery it must be said!
10 min There have been some very late challenges in the opening 10 minutes of this match, and Marcelo does not look comfortable following a tackle from Alves. The Brazilian's screams can be heard.
8 min Half-chance for the away side this time as Berchiche drives into a dangerous area inside the Real Madrid box, but the defender fires wide of the far post. Nervy work from Nacho there.
6 min Nervy moments inside the PSG box as Areola palms a Kroos corner back into the penalty box, and Marquinhos almost turns into his own net. Real Madrid have been much the better team thus far.
4 min Half-chance for Real Madrid as Ronaldo meets a long-range Isco pass inside the PSG box, but the attacker's effort was always drifting wide of the far post. The home side have started well.
3 min Neymar has just been chopped to the ground by Kroos and Casemiro. The first of many I suspect! Neymar came off the left to drift inside, but Kroos and Casemiro were not letting him pass.
2 min... it must be said that there is a wonderful atmosphere inside the stadium tonight. It has the feeling of a semi-final or a final, not a last-16 first leg. Let's hope that the match produces. Game on!
0 min KICKOFF! PSG kick things off in the Spanish capital...