The Parisian club has now won the prestigious cup on 14 separate times.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele opened the scoring in the opening stages.
Yet, the southern French side fired twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital equaliser in the final seconds to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all scored successfully for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the last 13 seasons.
