PSG has now won the season-opening cup on 14 different occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the net in the opening stages.
Yet, the southern French side fired two times late to seize a surprise lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker grabbed a vital equaliser in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a 4-1 penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last thirteen years.
