The Parisian club has now won the season-opening cup on 14 separate times.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after the French winger found the scoring early on.
However, the southern French side struck twice late to take a shock lead. Initially, the English forward scored from the penalty spot, before the defender unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the dying seconds to force the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the last thirteen years.
