PSG has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown featuring the Ligue 1 winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last 13 years.
