The Parisian club has now won the season-opening trophy on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side struck twice late to take a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last 13 seasons.
