PSG has now secured the season-opening cup on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a successful spot-kick decider to get past Marseille in the Gulf and capture a fourth straight French Super Cup title.
The Champions League holders appeared to be coasting towards a comfortable triumph in the showdown between the Ligue 1 winners and the French Cup winners after the French winger opened the net early on.
However, Marseille fired two times in the closing moments to seize a shock advantage. First, Mason Greenwood converted from the spot-kick, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking twist of events, the Portuguese striker snatched a crucial leveler in the final seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, stopping crucial attempts from Matt O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to complete a 4-1 penalty win.
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 trophy for the 12th time in the past thirteen seasons.
