PSG has now claimed the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
However, the southern French side struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned 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 moments to force the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last thirteen seasons.
