The Parisian club has now won the season-opening cup on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the match between the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side struck twice late to take a surprise lead. First, the English forward converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos snatched a vital equaliser in the final seconds to force the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the hero, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to seal a 4-1 penalty win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the last 13 seasons.
