The Parisian club has now won the prestigious trophy on 14 different times.
Paris Saint-Germain needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a straightforward win in the showdown between the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, Marseille fired two times late to seize a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout victory.
Now 14-time winners PSG, who faced 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.
