The Parisian club has now claimed the prestigious cup on fourteen separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the scoring early on.
However, Marseille fired two times in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a crucial leveler in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive attempts from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
