PSG has now won the prestigious trophy on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be coasting towards a straightforward 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.
However, Marseille struck twice in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions 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 competition for the twelfth time in the past thirteen seasons.
