The Parisian club has now secured the season-opening cup on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a shock lead. Initially, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past 13 seasons.
