PSG has now secured the season-opening trophy on 14 different occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side fired two times late to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for PSG to complete a convincing shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past 13 years.
