PSG has now secured the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time leveler followed by a perfect spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a straightforward win in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele found the net early on.
Yet, Marseille struck two times in the closing moments to take a surprise lead. Initially, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 penalty victory.
The record champions Paris Saint-Germain, 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 last 13 seasons.
