PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France holders after the French winger opened the net in the opening stages.
However, Marseille fired two times in the closing moments to seize a shock advantage. Initially, 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 events, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last thirteen seasons.
