The Parisian club has now won the season-opening trophy on fourteen separate times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
However, the southern French side fired two times late to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.