PSG has now secured the prestigious cup on fourteen separate occasions.
Paris Saint-Germain needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the French league winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, Marseille struck twice in the closing moments to take a shock lead. First, Mason Greenwood scored from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital leveler in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 years.
