The Parisian club has now claimed the season-opening cup on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the French league winners and the French Cup winners after the French winger opened the net in the opening stages.
However, the southern French side fired two times in the closing moments to take a shock lead. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 years.
