The Parisian club has now claimed the prestigious trophy on fourteen different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a comfortable triumph in the match featuring the Ligue 1 winners and the Coupe de France holders after Ousmane Dembele opened the net in the opening stages.
Yet, Marseille struck twice in the closing moments to seize a surprise advantage. First, the English forward scored from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, the Portuguese striker grabbed a crucial leveler in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and the young talent all converted with composure for PSG to complete a 4-1 shootout victory.
The record winners PSG, who faced last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the past 13 seasons.
