Propelled by the riches of their Qatari owners, PSG dream of following in Real's footsteps and becoming kings of Europe, a year after their humiliating exit in the last 16 at the hands of Barcelona.
On that occasion, having won 4-0 in the first leg, PSG collapsed in the return at the Camp Nou, going down 6-1.
"This is a chance for us to keep growing as a club by playing against the reigning champions and the team that has won the most titles. We want to get to that level," said PSG's Spanish coach Unai Emery ahead of Wednesday's last 16, first leg at the 81,000-seat Santiago Bernabeu, which kicks off at 1945 GMT.
Emery said his side -- who will be backed by 4,000 fans in the Spanish capital -- had learnt from that defeat a year ago and are "better prepared now".
The pressure on him is immense, with PSG's owners unlikely to look kindly on a second consecutive exit at this stage of the Champions League given the extent of their investment at the start of this season.
The mastermind of Barcelona's stunning comeback that night, Neymar, is now a PSG player, having cost the French club a world-record fee of 222 million euros ($264 million). They also committed 180 million euros to take 19-year-old striker Kylian Mbappe from Monaco.
"It is not easy to win a competition like this. We need to go through a lot of things on the way, but each season, and every day that goes by, we are working and getting closer to our objective," said PSG's Brazilian defender Marquinhos.
History on Real's side
If domestic form is anything to go by, then PSG look in great shape.
They have won 14 out of 15 games since the end of the Champions League group, while Real flounder in fourth place in La Liga, 17 points behind leaders Barcelona.
Just as Emery can ill afford a defeat over two legs -- the return will be in Paris on March 6 -- so Real coach Zinedine Zidane's future likely depends on the outcome of the tie.
"I am not thinking about my future. I am only thinking about the match," the Frenchman insisted on the eve of the game.
History is on Real's side -- they are the 12-time European champions, winners in each of the last two seasons.
In Cristiano Ronaldo, Madrid have the current Ballon d'Or and a player who has scored 99 times for them in the Champions League. The Portuguese has 43 goals in his last 43 appearances in the knockout phase.
Neymar, meanwhile, is seen by many in Madrid as the man Real president Florentino Perez should try to sign to succeed Ronaldo, now 33.
Marcelo, the Real left-back and an international colleague of the Brazilian forward, said at the weekend that he could see Neymar one day in the home dressing room at the Bernabeu.
Marquinhos, meanwhile, insisted Neymar is not unsettled by the speculation.
"He knows very well how to control his emotions. He handles the pressure and responds on the field," he said.
Mbappe is in the spotlight, too. The teenager is the youngest player to reach 10 Champions League goals -- and PSG beat Real to his signature last August.
PSG's front three of Neymar, Mbappe and Edinson Cavani have scored 70 goals between them, compared to 38 for Real's 'BBC' of Ronaldo, Gareth Bale and Karim Benzema.
"Neymar is a great player, but we have to think about the whole team, the collective is more important," said Marcelo.
PSG travelled without veteran midfielder Thiago Motta, meaning recent signing Lassana Diarra is tipped to start against his old club. For Real, Nacho should replace the banned Dani Caravajal at right-back.