The Parisian club has now claimed the prestigious cup on 14 different occasions.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders seemed to be sailing towards a comfortable triumph in the match featuring the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
Yet, the southern French side fired two times in the closing moments to seize a shock advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a 4-1 penalty win.
The record winners 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 thirteen seasons.
