PSG has now won the season-opening trophy on 14 different occasions.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, Marseille fired twice late to seize a shock advantage. 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 breathtaking twist of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen years.
