PSG has now claimed the season-opening cup on fourteen different occasions.
Paris Saint-Germain required a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward win in the match between the French league winners and the French Cup winners after the French winger found the net early on.
Yet, the southern French side struck twice in the closing moments to take a shock advantage. Initially, the English forward scored from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of fortune, the Portuguese striker snatched a vital equaliser in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping decisive kicks 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 penalty win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the last 13 seasons.
