The Parisian club has now won the prestigious trophy on fourteen separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The Champions League holders appeared to be sailing towards a straightforward win in the match featuring the French league winners and the French Cup holders after the French winger opened the scoring in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. First, the English forward converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker grabbed a vital equaliser in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for PSG to complete a convincing shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 years.