The Parisian club has now secured the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture 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 French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, the southern French side struck two times in the closing moments to seize a shock lead. First, Mason Greenwood scored from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable twist 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 stood as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
