PSG has now won the season-opening cup on fourteen different occasions.
The Parisian giants required a stoppage-time leveler followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a comfortable triumph in the match between the Ligue 1 winners and the French Cup winners after Ousmane Dembele found the scoring in the opening stages.
However, the southern French side fired two times in the closing moments to take a surprise advantage. Initially, Mason Greenwood scored from the spot-kick, before the defender unfortunately turned the ball into his own net for an own-goal.
In a breathtaking turn of fortune, the Portuguese striker grabbed a crucial leveler in the final seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then stood as the hero, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, the full-back, and the young talent all converted with composure for Paris Saint-Germain to seal a convincing penalty victory.
The record winners PSG, who faced last season's Ligue 1 runners-up Olympique de Marseille after achieving a league and cup double, have now lifted this trophy for the 12th time in the past 13 years.
