PSG has now secured the season-opening cup on 14 different times.
The Parisian giants needed a dramatic equaliser followed by a successful penalty shootout to overcome Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a comfortable triumph in the showdown featuring the French league champions and the French Cup winners after Ousmane Dembele opened the net early on.
However, the southern French side struck two times in the closing moments to seize a surprise lead. First, Mason Greenwood scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable turn of fortune, the Portuguese striker grabbed a crucial equaliser in the dying moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from Matt O'Riley and Traore.
In the shootout, Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for Paris Saint-Germain to complete a convincing penalty win.
Now 14-time champions PSG, who faced last season's Ligue 1 second-placed team Olympique de Marseille after completing a domestic double, have now won this competition for the twelfth time in the past 13 years.
