The Parisian club has now secured the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward win 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, the southern French side struck two times late to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the last thirteen years.
