The Parisian club has now secured the prestigious trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
Yet, the southern French side fired two times late to seize a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for PSG to complete a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.
