PSG has now won the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
However, Marseille struck twice late to seize a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker snatched a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 years.
