The Parisian club has now claimed the prestigious trophy on fourteen different times.
Paris Saint-Germain required a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, Marseille struck twice in the closing moments to take a surprise lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of events, Goncalo Ramos grabbed a vital leveler in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to seal a 4-1 shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.