PSG has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic leveler followed by a perfect penalty shootout to get past their arch-rivals in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 champions and the French Cup winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck twice late to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to force the contest into a deciding shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all scored successfully for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last 13 seasons.
