Roberto Firmino put his eye injury behind him and came off the bench to score Liverpool's winner on his 150th appearance for the reds.
The reds dominated the game from the first whistle and were unlucky to be heading into injury time with the scores 2-2, before Firmino's goal ensured the points went our way.
Firmino's eye injury sustained against Spurs at the weekend meant he was only good enough to be named on the bench - Daniel Sturridge making his first Champions League start for 5 years.
In midfield, Naby Keita was rested and in came the captain Jordan Henderson to replace him.
For PSG, they had the talent of Neymar and Kylian Mbappe to come in alongside Edinson Cavani.
The reds, kicking to the Kop in the first half after losing the toss, had racked up 6 corners by the 15th minute - with the players focussing on unsettling the away side's keeper Alphonse Areola.
Van Dijk and Sadio Mane two of the players who got testing shots away during this period.
Thiago Silva was called into action to stop a great through ball from Milner arriving at Mane's feet. At the other end Neymar had a chance fired at Alisson, and they arguably should have done better from a counter attack when Kylian Mbappe's crossfield pass completely missed his strike partners.
On the half hour Liverpool got the opening goal they had deserved.
Trent Alexander-Arnold sending in a cross from the right that nobody could get hold of. It went straight across to Andy Robertson and this time his cross was met by the powerful head of Daniel Sturridge. 1-0. Wriggly arms time.
Within 6 minutes the reds had doubled the lead.
Wijnaldum, who was excellent again, was fouled in the area and James Milner stepped up to smash in another penalty.
But with half time approaching Thomas Meunier grabbed a goal back after a ball into the Liverpool area took an unfortunate bounce off Andy Robertson. He was in the right place to volley the ball into the net.
'We go again'
But the reds came back out in the second half with the right attitude and continued to dominate the game.
Just before the hour Mo Salah thought he had Liverpool's third, but seconds later the goal was ruled out for a foul by Daniel Sturridge on the PSG keeper.
With 20 minutes remaining, Sturridge made way for Bobby Firmino but it was PSG who would get an equaliser with their first shot on target of the half.
Mo Salah giving away the ball in the middle of Liverpool's half and the ball quickly made it's way to Mbappe in the box who put the easy chance away.
It was set to be a harsh point for the reds but as the clock ticked past 90 minutes Firmino, at the corner of the box, twisted and turned before sticking the ball in the opposite corner.
What a winner, and what a way for the reds to start their European campaign.
Six consecutive wins for the reds in all competitions and with Napoli and Red Star drawing, LFC sit at the top of the group for now.