The Parisian club has now secured the season-opening trophy on fourteen separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect penalty shootout 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 winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, the southern French side struck two times in the closing moments to seize a shock lead. Initially, 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 turn of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past 13 seasons.
