The Parisian club has now claimed the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the net early on.
Yet, Marseille struck two times in the closing moments to take a shock advantage. Initially, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to send the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a convincing penalty win.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past thirteen years.