The Parisian club has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side fired twice in the closing moments to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a vital leveler in the dying moments to send the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a convincing penalty victory.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen seasons.