The Parisian club has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille struck two times in the closing moments to take a shock advantage. First, Mason Greenwood converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker grabbed a crucial leveler in the dying moments to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a convincing penalty win.
Now 14-time 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 trophy for the twelfth time in the past thirteen years.
