The Parisian club has now won the season-opening trophy on 14 separate occasions.
Paris Saint-Germain required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions appeared to be sailing towards a comfortable win in the match featuring the French league champions and the French Cup holders after Ousmane Dembele found the net early on.
However, Marseille struck twice in the closing moments to take a shock lead. 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 remarkable turn of fortune, Goncalo Ramos snatched a vital equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving decisive kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all converted successfully for Paris Saint-Germain to complete a convincing shootout victory.
Now 14-time champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen years.
