PSG has now won the prestigious cup on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the scoring in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock advantage. Initially, 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 turn of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a 4-1 penalty win.
Now 14-time champions 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.