The Parisian club has now secured the season-opening trophy on 14 different occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The European champions seemed to be sailing towards a straightforward win in the match between the Ligue 1 winners and the French Cup holders after the French winger found the net early on.
However, the southern French side struck twice late to seize a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos grabbed a vital leveler in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to complete a 4-1 penalty win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past thirteen seasons.