The Parisian club has now won the prestigious cup on 14 different occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a straightforward win in the showdown featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
Yet, the southern French side fired twice in the closing moments to take a surprise advantage. First, the English forward converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos snatched a crucial leveler in the final moments to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 seasons.
