PSG has now won the prestigious cup on fourteen different occasions.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the showdown between the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a shock lead. Initially, the English forward scored from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, the full-back, and the young talent all converted successfully for PSG to complete a convincing penalty victory.
The record winners PSG, who faced 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 thirteen seasons.
