The Parisian club has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be coasting towards a straightforward triumph in the showdown between the French league winners and the Coupe de France holders after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice late to take a surprise advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty win.
Now 14-time winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the past 13 years.
