The Parisian club has now claimed the season-opening cup on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele found the net early on.
Yet, Marseille struck two times in the closing moments to seize a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout victory.
The record 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 competition for the twelfth time in the past 13 seasons.
