The Parisian club has now won the prestigious cup on fourteen separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup holders after the French winger opened the net early on.
However, Marseille fired twice in the closing moments to take a surprise lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the past thirteen years.
