PSG has now secured the prestigious trophy on fourteen separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a perfect penalty shootout to get past Marseille in Kuwait and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders appeared to be sailing towards a straightforward triumph in the showdown between the French league winners and the French Cup winners after Ousmane Dembele opened the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock advantage. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final moments to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a 4-1 penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past thirteen seasons.
