The Parisian club has now secured the prestigious cup on 14 different occasions.
The Parisian giants required a dramatic leveler followed by a perfect penalty shootout to overcome their arch-rivals in Kuwait and secure a record-extending fourth consecutive French Super Cup title.
The Champions League holders appeared to be coasting towards a straightforward triumph in the match featuring the French league winners and the Coupe de France winners after Ousmane Dembele opened the net in the opening stages.
However, Marseille fired twice late to seize a shock advantage. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a vital leveler in the final moments to force the contest into a deciding shootout. PSG goalkeeper Lucas Chevalier then emerged as the key figure, stopping crucial 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 win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the twelfth time in the last 13 years.
