PSG has now won the prestigious cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the match featuring the French league champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice late to take a surprise lead. Initially, the English forward converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to send the match 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 the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.
