PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in Kuwait and secure a fourth straight French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the French league winners and the Coupe de France holders after Ousmane Dembele opened the net early on.
Yet, Marseille fired twice in the closing moments to take a shock advantage. First, Mason Greenwood scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a remarkable twist of events, the Portuguese striker snatched a vital leveler in the dying seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted with composure for Paris Saint-Germain to seal a convincing shootout victory.
The record champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a domestic double, have now won this competition for the 12th time in the last 13 seasons.
