The Parisian club has now won the season-opening trophy on fourteen different occasions.
The Parisian giants required a stoppage-time equaliser followed by a successful penalty shootout to get past their arch-rivals in the Gulf and secure a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the showdown between the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired twice late to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a 4-1 shootout victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past thirteen seasons.
