The Parisian club has now secured the prestigious trophy on 14 separate occasions.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown featuring the French league champions and the Coupe de France holders after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side fired twice in the closing moments to seize a surprise lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker grabbed a vital leveler in the dying moments to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the 12th time in the last 13 seasons.
