PSG has now claimed the prestigious trophy on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward win in the match between the Ligue 1 winners and the Coupe de France holders after the French winger found the net in the opening stages.
Yet, Marseille fired two times late to take a shock lead. First, the English forward scored from the spot-kick, before the defender inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of fortune, the Portuguese striker snatched a vital equaliser in the final seconds to force the contest 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 converted with composure for PSG to complete a convincing shootout win.
The record champions Paris Saint-Germain, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this trophy for the twelfth time in the past 13 years.
