The Parisian club has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the scoring early on.
Yet, the southern French side struck two times late to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past 13 seasons.
