The Parisian club has now claimed the season-opening cup on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be sailing towards a straightforward triumph in the showdown featuring the French league winners and the French Cup holders after the French winger found the net in the opening stages.
Yet, the southern French side struck twice late to seize a surprise advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a crucial leveler in the dying seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty win.
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 last 13 seasons.
