The Parisian club has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required 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 sailing towards a comfortable win in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck two times late to seize a shock advantage. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last 13 years.