PSG has now won the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be coasting towards a straightforward triumph in the match between the French league winners and the French Cup winners after Ousmane Dembele found the scoring early on.
Yet, Marseille fired twice late to take a surprise advantage. First, the English forward 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 fortune, Goncalo Ramos grabbed a vital equaliser in the dying moments to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after achieving a domestic double, have now won this trophy for the twelfth time in the last 13 years.
