The Parisian club has now secured the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side fired twice late to seize a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the last thirteen years.
