In a repeat of last year’s Club World Cup final, PSG looked determined to avenge that defeat and start on the front foot against Liam Rosenior’s men.
It was a high-octane opening 10 minutes at the Parc des Princes, and after both sides missed a couple of half-chances, the Parisians broke the deadlock when Joao Neves’ cushioned header at the back post was clinically fired home by Bradley Barcola via the underside of the bar.
The hosts went in pursuit of a quickfire second, and they came within inches of doubling their lead, as Ousmane Dembele’s powerful strike was parried onto the post by Filip Jorgensen.
Grateful for that narrow reprieve, Chelsea responded with Pedro Neto seeing a dangerous cutback saved by Matvey Safonov, while at the other end, Jorgensen reacted superbly to thwart a curled effort from Barcola.
The visitors continued to improve as the first half progressed, and their pressure paid dividends when Enzo Fernandez’s cross-field pass picked out Malo Gusto, who drove a smart finish through the body of Safonov to restore parity.
The end-to-end nature of the contest showed no signs of slowing down with half-time approaching, and Dembele duly broke on the counter before finishing expertly beyond Jorgensen to put PSG back in front - just a mere 15 seconds after Cole Palmer had missed a glorious opportunity himself.
Chelsea were hoping to stretch a six-game winning run against French opposition in the UCL, and they looked to up the ante at the start of the second period.
Rosenior’s side remained a threat in the final third, and an equaliser soon arrived in the 57th minute when a superb run and cross from Neto was clinically dispatched by Fernandez for his 12th goal of the season.
That set up a fascinating final half-hour in the French capital, with PSG boss Luis Enrique calling on Khvicha Kvaratskhelia and Lee Kang-In from the hosts’ bench.
Kvaratskhelia was heavily involved as the Parisians went ahead for the third time of the night, as the Georgian unselfishly set up Vitinha for a sublime lobbed finish after a calamitous mistake from Jörgensen in the Blues’ goal.
Chelsea thought they’d drawn level once again when Joao Pedro tucked home from close range, only for the Brazilian to be denied by the offside flag.
Those fine margins proved to be costly, with PSG adding a fourth goal in the 86th minute through super-sub Kvaratskhelia, who cut inside from the left flank and curled a spectacular finish into the far corner to send the Parc des Princes into bedlam.
The visitors looked shell-shocked by that goal, and PSG capitalised by adding a fifth in the final minute of stoppage time, with Kvaratskhelia finding himself in the right place at the right time to finish from Achraf Hakimi’s cross to give Enrique’s men a commanding first-leg advantage.
Flashscore Man of the Match: Khvicha Kvaratskhelia (Paris Saint-Germain)