The Parisian club has now claimed the season-opening cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring early on.
However, the southern French side struck twice in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a convincing shootout win.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 years.
