The Parisian club has now won the prestigious cup on fourteen different times.
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 Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France winners after the French winger opened the scoring early on.
However, Marseille struck two times late to take a surprise advantage. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored successfully for PSG to complete a convincing shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
