The Parisian club has now won the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the Ligue 1 champions and the Coupe de France holders after the French winger opened the scoring in the opening stages.
However, the southern French side fired twice late to take a shock lead. First, Mason Greenwood scored from the penalty spot, 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 crucial leveler in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the key figure, stopping crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 penalty victory.
Now 14-time winners PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now won this competition for the 12th time in the past 13 seasons.
