The Parisian club has now claimed the season-opening trophy on fourteen different times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the match between the French league winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
However, Marseille struck twice late to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a convincing shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this trophy for the twelfth time in the past thirteen seasons.
