The Parisian club has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward win in the match between the French league winners and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, Marseille struck twice late to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a vital leveler in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this competition for the 12th time in the last thirteen years.
