PSG has now secured the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 champions and the Coupe de France holders after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck two times in the closing moments to seize a shock lead. Initially, the English forward converted from the spot-kick, before Willian Pacho unfortunately 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 seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the past 13 years.
