The Parisian club has now secured the season-opening cup on 14 different times.
Paris Saint-Germain needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele opened the scoring early on.
Yet, the southern French side struck twice in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the past thirteen years.
