PSG has now won the season-opening trophy on 14 separate times.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to get past their arch-rivals in the Gulf and capture a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a comfortable win in the match featuring the French league 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 in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the final moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
