PSG has now claimed the season-opening cup on fourteen different times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the French league champions and the French Cup holders after the French winger opened the net in the opening stages.
Yet, Marseille fired two times late to take a shock advantage. Initially, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who met 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 years.
