PSG has now won the season-opening cup on 14 separate times.
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 seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele opened the net early on.
However, the southern French side fired two times in the closing moments to take a surprise advantage. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a breathtaking turn of events, the Portuguese striker snatched a vital equaliser in the final seconds to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping crucial attempts from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past thirteen years.
