PSG has now claimed the prestigious cup on 14 separate times.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive French Super Cup title.
The European champions seemed to be coasting towards a comfortable triumph in the match between the Ligue 1 winners and the Coupe de France holders after the French winger opened the net early on.
However, Marseille struck two times in the closing moments to take a shock advantage. Initially, the English forward scored from the spot-kick, before the defender inadvertently turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Traore.
From the spot, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for PSG to complete a 4-1 shootout win.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this trophy for the twelfth time in the last thirteen years.