PSG has now claimed the season-opening trophy on 14 separate occasions.
The Parisian giants required a stoppage-time leveler followed by a successful spot-kick decider to get past Marseille in the Gulf and secure a fourth straight Trophee des Champions title.
The European champions appeared to be coasting towards a straightforward triumph in the showdown between the Ligue 1 winners and the French Cup holders after the French winger opened the scoring early on.
However, the southern French side struck twice in the closing moments to take a surprise advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately directed the ball into his own net for an own-goal.
In a breathtaking twist of events, the Portuguese striker grabbed a vital equaliser in the dying seconds to force the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
From the spot, Ramos, Vitinha, the full-back, and the young talent all converted with composure for PSG to seal a convincing shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 runners-up Olympique de Marseille after completing a league and cup double, have now lifted this trophy for the 12th time in the last 13 seasons.
