PSG has now won the season-opening cup on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a comfortable win in the match between the French league winners and the French Cup holders after Ousmane Dembele opened the net early on.
Yet, the southern French side struck two times in the closing moments to take a shock lead. Initially, the English forward converted from the spot-kick, before the defender unfortunately directed the ball into his own net for an own goal.
In a remarkable turn of events, 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, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a convincing shootout victory.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 years.
