The Parisian club has now secured the prestigious cup on 14 separate times.
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 victory.
The European champions appeared to be sailing towards a comfortable win in the showdown between the French league champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, the southern French side struck twice late to take a surprise lead. First, the English forward converted 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 snatched a vital equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for PSG to complete a convincing penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
