The Parisian club has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille fired twice in the closing moments to take a surprise advantage. Initially, the English forward scored from the spot-kick, 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 seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for PSG to complete a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.
