PSG has now won the season-opening cup on 14 separate 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 comfortable triumph in the showdown featuring the French league champions and the French Cup winners after the French winger opened the net in the opening stages.
However, the southern French side fired two times in the closing moments to seize a shock advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a vital leveler in the final moments to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, saving crucial attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past thirteen seasons.
