The Parisian club has now claimed the season-opening cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the Ligue 1 champions and the Coupe de France winners after the French winger opened the scoring early on.
However, Marseille fired two times late to take a surprise lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital equaliser in the final seconds to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 years.
