PSG has now claimed the season-opening cup on 14 separate occasions.
Paris Saint-Germain required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup title.
The Champions League holders seemed to be sailing towards a comfortable win in the showdown featuring the French league champions and the Coupe de France winners after Ousmane Dembele found the scoring in the opening stages.
However, Marseille fired two times late to take a shock lead. First, Mason Greenwood scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of fortune, the Portuguese striker snatched a crucial leveler in the final moments to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past thirteen years.
