PSG has now claimed the season-opening cup on 14 different occasions.
Paris Saint-Germain needed a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a comfortable triumph in the match featuring the Ligue 1 winners and the French Cup holders after Ousmane Dembele found the net early on.
Yet, Marseille fired twice late to seize a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a crucial leveler in the dying seconds to force the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
From the spot, Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time champions Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now won this competition for the twelfth time in the past thirteen years.