The reigning Ligue 1 champions took the scenic route to this stage via the playoffs, but they swept aside Brest with consummate ease, demolishing their French counterparts 10-0 on aggregate to book a date with Liverpool.
In contrast, Arne Slot's men were the best team in the continent during the league phase, topping the 36-team standings with 21 points from a possible 24 after winning their first seven games of the new edition.
Here, Sports Mole takes an in-depth look at the head-to-head record and previous meetings between the two sides.
Head-to-head record
Previous meetings: 4
PSG wins: 2
Draws: 0
Liverpool wins: 2
Nothing can separate Paris Saint-Germain and Liverpool in the head-to-head column heading into Wednesday's first leg, as both sides boast two wins apiece from their four previous meetings in European competition so far.
The Reds' journey to Champions League glory in the 2018-19 season actually commenced with victory over Thomas Tuchel's PSG, who visited Anfield for their opening group-stage showdown but came out on the wrong end of a 3-2 scoreline.
Les Parisiens had seemingly done enough for a point as Kylian Mbappe punished Liverpool's inability to kill the game off, but Roberto Firmino came off the bench to net a last-gasp winner in front of the fervent away crowd.
However, PSG had their revenge a couple of months later, conquering Liverpool 2-1 at the Parc des Princes as the electrifying attack of Edison Cavani, Neymar and Mbappe ran Jurgen Klopp's backline ragged.
PSG and Liverpool's 2018-19 Champions League reunion marked just the second time that the two continental giants had met in competitive action, having first crossed paths during the semi-finals of the 1996-97 European Cup Winners' Cup.
The first-ever meeting between Les Parisiens and the Reds was not much of a contest, as PSG stormed to a 3-0 win in the first leg of that semi-final courtesy of goals from Leonardo, Benoit Cauet and Jerome Leroy.
Roy Evans's Liverpool threatened an almighty second-leg turnaround at Anfield two weeks later, as Robbie Fowler and Mark Wright breached the Parisiens' backline, but PSG still prevailed 3-2 on aggregate before losing to Barcelona in the final.
Having netted penalties in both of Liverpool's clashes with PSG in the 2018-19 season, James Milner is the highest individual scorer in this fixture with two strikes to his name.
Last four meetings
Nov 28, 2018: PSG 2-1 Liverpool (Champions League Group Stage)
Sep 18, 2018: Liverpool 3-2 PSG (Champions League Group Stage)
Apr 24, 1997: Liverpool 2-0 PSG (UEFA Cup Winners' Cup Semi-Final Second Leg)
Apr 10, 1997: PSG 3-0 Liverpool (UEFA Cup Winners' Cup Semi-Final First Leg)
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Written by
Ben Knapton