PSG has now won the season-opening cup on 14 different times.
The Parisian giants needed a stoppage-time equaliser followed by a perfect spot-kick decider to get past Marseille in the Gulf and capture a fourth straight Trophee des Champions victory.
The Champions League holders seemed to be coasting towards a straightforward triumph in the showdown between the French league champions and the Coupe de France winners after Ousmane Dembele found the net early on.
However, the southern French side fired twice in the closing moments to take a surprise advantage. First, the English forward converted from the penalty spot, 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 vital equaliser in the final moments to send the contest into a penalty shootout. PSG goalkeeper Chevalier then stood as the key figure, saving decisive attempts from Matt O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and Desire Doue all converted with composure for Paris Saint-Germain to seal a 4-1 shootout win.
The record champions PSG, who faced last season's Ligue 1 runners-up Marseille after completing a league and cup double, have now won this competition for the twelfth time in the last thirteen years.
