The Parisian club has now claimed the prestigious trophy on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France holders after the French winger opened the net early on.
Yet, the southern French side fired two times late to seize a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker snatched a vital leveler in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last thirteen years.
