PSG has now won the season-opening trophy on 14 different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille 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 showdown featuring the French league champions and the French Cup winners after the French winger opened the scoring in the opening stages.
However, Marseille fired two times late to seize a surprise lead. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently 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 seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
