The Parisian club has now secured the prestigious cup on 14 separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to take a shock lead. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned 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 seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this competition for the twelfth time in the past thirteen years.
