The Parisian club has now won the season-opening cup on fourteen different times.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck two times late to take a shock lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial equaliser in the final moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for PSG to seal a 4-1 penalty win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past 13 years.
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