The Parisian club has now won the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a comfortable triumph in the match between the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille fired twice in the closing moments to take a surprise advantage. First, Mason Greenwood 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, the Portuguese striker grabbed a crucial equaliser in the final moments to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, 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 winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 years.
