PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
