PSG has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the match featuring the French league winners and the French Cup holders after the French winger opened the net in the opening stages.
Yet, the southern French side fired two times in the closing moments to seize a surprise lead. First, the English forward scored from the spot-kick, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a vital equaliser in the dying moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored successfully for Paris Saint-Germain to complete a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now won this competition for the twelfth time in the past thirteen years.