The Parisian club has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times late to take a surprise advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for PSG to complete a convincing shootout win.
The record winners PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
