PSG has now won the prestigious trophy on fourteen separate times.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired twice late to seize a shock advantage. Initially, 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, the Portuguese striker grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to seal a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
