PSG has now secured the season-opening trophy on fourteen separate occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in Kuwait and capture 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 Coupe de France holders after Ousmane Dembele opened the scoring early on.
However, Marseille struck twice in the closing moments to take a surprise advantage. First, the English forward converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a breathtaking turn of events, Goncalo Ramos grabbed a vital leveler in the final moments to send the match into a penalty shootout. PSG goalkeeper Lucas Chevalier then stood as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 penalty win.
The record winners PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 years.
