The Parisian club has now won the season-opening cup on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable win in the match featuring the French league winners and the Coupe de France winners after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired twice late to take a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the 12th time in the past thirteen seasons.
