PSG has now claimed the season-opening trophy on fourteen separate occasions.
The Parisian giants needed a stoppage-time leveler followed by a perfect penalty shootout to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 champions and the French Cup holders after Ousmane Dembele found the net in the opening stages.
However, Marseille struck two times in the closing moments to seize a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable turn of events, Goncalo Ramos snatched a vital leveler in the dying seconds to send the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, saving decisive kicks from Matt O'Riley and Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all scored with composure for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last 13 years.