The Parisian club has now claimed the prestigious trophy on fourteen separate times.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a comfortable win in the showdown between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, Marseille struck two times in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital leveler in the final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the past thirteen years.
