The Parisian club has now secured the prestigious cup on fourteen separate occasions.
The Parisian giants required a dramatic leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net early on.
However, Marseille fired two times in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for PSG to seal a convincing shootout win.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past thirteen seasons.
