The Parisian club has now secured the prestigious trophy on fourteen different occasions.
The Parisian giants required a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos grabbed a crucial equaliser in the final moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen years.