The Parisian club has now won the prestigious cup on fourteen different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, the southern French side fired two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 years.