PSG has now won the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a successful 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 coasting towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele opened the scoring early on.
However, the southern French side struck two times late to seize a shock lead. First, the English forward scored from the penalty spot, before Willian Pacho inadvertently 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 dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and the young talent all scored successfully for Paris Saint-Germain to seal a 4-1 penalty win.
The record champions Paris Saint-Germain, who faced last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this trophy for the 12th time in the past 13 seasons.
