The Parisian club has now won the prestigious cup on fourteen different times.
The Parisian giants required a dramatic leveler followed by a successful penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions seemed to be coasting towards a straightforward triumph in the match featuring the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to take a surprise advantage. First, the English forward converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a vital leveler in the final seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted with composure for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the 12th time in the past 13 years.