PSG has now claimed the prestigious cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a successful penalty shootout to overcome their arch-rivals in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the match featuring the Ligue 1 champions and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
Yet, Marseille fired twice in the closing moments to take a shock advantage. First, the English forward scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of events, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for PSG to seal a 4-1 penalty victory.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now lifted this trophy for the 12th time in the last thirteen years.
