PSG has now secured the prestigious cup on fourteen different times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side struck twice late to seize a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker snatched a vital leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
