The Parisian club has now won the season-opening cup on 14 different times.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a comfortable win in the showdown featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, Marseille fired two times in the closing moments to seize a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.
