The Parisian club has now secured the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The Champions League holders seemed to be coasting towards a comfortable win in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice late to take a shock advantage. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos snatched a vital leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to seal a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 years.
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