The Parisian club has now claimed the prestigious trophy on 14 separate times.
The Parisian giants needed a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions seemed to be sailing towards a comfortable triumph in the match featuring the French league winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital leveler in the final seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing penalty win.
The record champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 years.
