The Parisian club has now claimed the prestigious cup on 14 different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side fired twice 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 equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
