The Parisian club has now claimed the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the French league champions and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, Marseille struck two times late to take a surprise lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital equaliser in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the 12th time in the past 13 years.
