The Parisian club has now won the prestigious trophy on fourteen different times.
Paris Saint-Germain required 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 Champions League holders appeared to be sailing towards a comfortable win in the showdown between the French league winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a surprise lead. Initially, 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 remarkable turn of events, the Portuguese striker snatched a vital leveler in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen years.
