PSG has now won the prestigious trophy on fourteen different occasions.
Paris Saint-Germain needed a dramatic leveler followed by a successful spot-kick decider to overcome Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the match between the Ligue 1 champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a shock lead. First, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker grabbed a vital leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the past 13 seasons.