The Parisian club has now won the prestigious cup on 14 separate times.
Paris Saint-Germain needed a stoppage-time equaliser followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the scoring early on.
However, Marseille fired two times in the closing moments to take a surprise lead. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial equaliser in the final seconds to send the match into a penalty shootout. The Parisian shot-stopper Chevalier then emerged as the hero, stopping crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to complete a convincing shootout victory.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last 13 years.
