The Parisian club has now secured the season-opening trophy on 14 separate occasions.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the match between the French league champions and the Coupe de France holders after the French winger opened the net in the opening stages.
Yet, Marseille struck two times in the closing moments to take a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.