The Parisian club has now claimed the season-opening trophy on 14 separate times.
Paris Saint-Germain required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a comfortable win in the match between the French league winners and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side struck twice in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently turned the ball into his own net for an own-goal.
In a breathtaking twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored with composure for PSG to complete a 4-1 shootout victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now won this trophy for the twelfth time in the last 13 years.