The Parisian club has now claimed the season-opening trophy on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be coasting towards a straightforward triumph in the showdown featuring the French league winners and the Coupe de France holders after the French winger found the net early on.
However, the southern French side struck twice in the closing moments to take a shock advantage. Initially, 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 events, Goncalo Ramos snatched a vital equaliser in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a domestic double, have now won this competition for the 12th time in the last 13 seasons.
