The Parisian club has now won the season-opening cup on 14 different occasions.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable win in the match between the Ligue 1 champions and the French Cup holders after the French winger opened the net in the opening stages.
Yet, Marseille struck two times in the closing moments to take a shock advantage. Initially, 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 breathtaking twist of events, the Portuguese striker snatched a vital leveler in the final moments to force the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to seal a 4-1 shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
