PSG has now won the prestigious cup on 14 different times.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the French league winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, the southern French side struck twice late to take a surprise lead. Initially, Mason Greenwood converted from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
