The Parisian club has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial leveler in the dying moments to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.