PSG has now won the prestigious cup on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a comfortable triumph in the showdown featuring the French league winners and the French Cup winners after Ousmane Dembele found the scoring early on.
However, the southern French side fired twice late to take a surprise lead. First, 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, the Portuguese striker snatched a vital leveler in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the past 13 seasons.
