PSG has now claimed the prestigious cup on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to get past their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the showdown between the French league winners and the Coupe de France holders after the French winger found the net in the opening stages.
However, the southern French side fired two times late to take a shock advantage. First, the English forward converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital leveler in the final moments to force the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the 12th time in the last thirteen seasons.
