PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck twice late to seize a shock lead. Initially, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial equaliser in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 years.
