The Parisian club has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the match featuring the French league champions and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice in the closing moments to seize a surprise 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 remarkable twist of fortune, Goncalo Ramos snatched a crucial leveler in the dying moments to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
