PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the French league champions and the French Cup holders after the French winger found the scoring in the opening stages.
Yet, the southern French side struck two times late to seize a surprise advantage. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing shootout win.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 seasons.
