The Parisian club has now won the prestigious trophy on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions victory.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the French league champions and the French Cup holders after Ousmane Dembele opened the net early on.
However, the southern French side fired twice in the closing moments to take a surprise advantage. Initially, the English forward converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a crucial leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
The record champions PSG, who faced last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen seasons.
