The Parisian club has now won the season-opening trophy on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, the southern French side fired two times late to seize a shock advantage. Initially, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a vital leveler in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to complete a convincing shootout win.
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 12th time in the last 13 years.
