PSG has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants required a dramatic equaliser followed by a successful penalty shootout to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the showdown featuring the French league champions and the French Cup holders after the French winger found the net in the opening stages.
However, Marseille fired two times in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.
