The Parisian club has now claimed the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the French league winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck two times in the closing moments to seize a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 years.