PSG has now won the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the French league champions and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past thirteen years.
