The Parisian club has now claimed the season-opening trophy on fourteen different times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward win in the match featuring the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
Yet, the southern French side struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a vital leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a 4-1 shootout win.
Now 14-time champions Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Olympique de Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the past 13 seasons.
