PSG has now claimed the prestigious cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, the southern French side struck two times late to take a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital equaliser in the final moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing shootout victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen years.