PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants needed a dramatic equaliser followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup winners after the French winger found the scoring in the opening stages.
Yet, the southern French side struck twice in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker snatched a crucial leveler in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 seasons.
