The Parisian club has now claimed the prestigious cup on fourteen different times.
The Parisian giants needed a dramatic leveler followed by a perfect 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 sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice late to take a surprise lead. First, the English forward scored from the spot-kick, before the defender unfortunately turned 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 seconds to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for PSG to complete a convincing penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now lifted this competition for the 12th time in the past 13 years.