The Parisian club has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a stoppage-time leveler 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 sailing towards a comfortable win in the showdown featuring the French league winners and the French Cup holders after the French winger found the scoring early on.
Yet, the southern French side fired twice in the closing moments to take a shock advantage. First, Mason Greenwood scored from the penalty spot, before Willian Pacho unfortunately 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 attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete 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 league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
