The Parisian club has now won the season-opening trophy on 14 different occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the match featuring the French league champions and the Coupe de France winners after the French winger opened the scoring in the opening stages.
However, Marseille struck twice in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a crucial equaliser in the final seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored with composure for PSG to seal a 4-1 shootout win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past thirteen years.