The Parisian club has now secured the prestigious trophy on 14 separate times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match between the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired two times in the closing moments to take a shock advantage. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the dying moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
