PSG has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain needed a dramatic 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 Champions League holders appeared to be coasting towards a straightforward triumph in the match between the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the net early on.
Yet, the southern French side struck twice in the closing moments to seize a surprise advantage. Initially, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a crucial equaliser in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now lifted this trophy for the twelfth time in the last thirteen seasons.
