Both teams had a host of chances in the second half, but it was Adil Rami who scored in the final minute to hand Valencia hope ahead of the second leg.
Here Sports Mole dissects the 90 minutes of action between the two Champions League rivals.
On target: 2
On target: 8
Was the result fair?
There is no question that PSG deserve to take a lead into the second leg. Valencia dominated possession throughout the evening, but the fact that they managed just two attempts on goal is a clear indication of their attacking threat. In truth, the away side could and should have been out of sight with a number of chances in the second half, but Valencia now have a glimmer of hope following that late strike from Rami.
The Spanish side's commitment and willingness to work will not be called into question this evening, but unfortunately they just lacked that quality in the final third. However, that late strike from Rami, in addition to Zlatan Ibrahimovic's red card, has given them real hope. One thing is for certain, they will need to play better in the second leg to have a chance of progressing.
It was just about the perfect away performance from the French outfit, until the last couple of moments, when they lost a goal and a man. That aside, it is hard not to be impressed by their overall display. They looked solid in defence with Alex on hand to make a number of fine blocks, while they have a host of tidy technicians in midfield. With some bookmakers offering odds of 25/1 for them to win the competition, you could certainly do a lot worse.
Sports Mole's man of the match
Lucas Moura: It is easy to see why every major European club coveted the Brazilian in the summer. He was simply sensational this evening as he continued to weave his way into the Valencia box, setting up his side's second goal. He came off early in the second period, but the damage had already been done.
Biggest gaffe of the match
Vicente Guaita had a bit of a horror show in the first period. He was at fault for both goals as he allowed a Lavezzi strike to squeeze through his palms, before getting in a mess with Pastore's effort. Granted, both shots were powerful, but the Spaniard simply had to do better.
Paolo Tagliavento had a fairly straightforward 90 minutes of action this evening. He was prepared to stop play when necessary, but was not overly concerned with awarding a free kick each time a foul was committed. Neither team will have had many complaints about his performance.
Valencia: The Spanish outfit return to domestic action at home to Real Mallorca on Sunday before travelling to face Real Zaragoza one week later.
PSG: The Ligue 1 outfit also return to league action this weekend with an away match against Sochaux before hosting Marseille one week later.