The Parisian club has now secured the season-opening cup on fourteen separate occasions.
The Parisian giants needed a dramatic leveler followed by a successful penalty shootout to overcome Marseille in Kuwait and capture a fourth straight 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 holders after Ousmane Dembele found the net in the opening stages.
Yet, Marseille fired two times in the closing moments to take a shock advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to complete a 4-1 penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen seasons.