The Parisian club has now secured the prestigious trophy on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille fired two times late to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial equaliser in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last 13 seasons.
