PSG has now claimed the season-opening cup on 14 separate times.
The Parisian giants required a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions title.
The European champions seemed to be sailing towards a straightforward win in the match featuring the Ligue 1 champions and the French Cup holders after the French winger found the net in the opening stages.
Yet, the southern French side struck two times in the closing moments to take a shock lead. First, the English forward converted from the spot-kick, before Willian Pacho inadvertently directed the ball into his own net for an own-goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial leveler in the final seconds to force the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial attempts from Matt O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a 4-1 penalty win.
Now 14-time champions PSG, who met last season's Ligue 1 second-placed team Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last thirteen years.
