The Parisian club has now claimed the season-opening trophy on 14 different times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider 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 match featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck two times late to seize a shock advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive attempts from Matt O'Riley and Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a 4-1 penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now lifted this competition for the 12th time in the past 13 years.