PSG has now claimed the prestigious trophy on 14 separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a successful spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger found the net early on.
Yet, Marseille struck two times late to take a shock 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 twist of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to force the match into a deciding shootout. The Parisian shot-stopper Lucas 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 converted with composure for Paris Saint-Germain to complete a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now won this competition for the 12th time in the last 13 years.
