The Parisian club has now won the season-opening trophy on 14 separate times.
The Parisian giants required a dramatic leveler followed by a perfect spot-kick decider to get past their arch-rivals in Kuwait and secure a fourth straight French Super Cup title.
The European champions appeared to be coasting towards a straightforward win in the showdown between the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
Yet, the southern French side fired twice late to take a shock lead. First, the English forward scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital leveler in the final seconds to force the match into a penalty shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, Vitinha, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a 4-1 shootout victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the last thirteen years.
