PSG has now secured the season-opening trophy on fourteen separate times.
The Parisian giants required a stoppage-time leveler followed by a successful penalty shootout to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions title.
The European champions appeared to be sailing towards a comfortable triumph in the showdown between the Ligue 1 champions and the French Cup holders after the French winger opened the scoring early on.
However, the southern French side fired two times late to seize a shock lead. Initially, Mason Greenwood scored from the penalty spot, before the defender inadvertently turned the ball into his own net for an own goal.
In a breathtaking turn of events, Goncalo Ramos snatched a crucial leveler in the final seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from O'Riley and Traore.
In the shootout, Goncalo Ramos, the midfielder, the full-back, and Desire Doue all scored successfully for Paris Saint-Germain to seal a 4-1 shootout win.
The record winners PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the past 13 seasons.