PSG has now secured the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 champions and the French Cup winners after the French winger opened the net early on.
However, the southern French side fired two times late to take a shock lead. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the past thirteen years.
