PSG has now claimed the season-opening trophy on 14 separate times.
The Parisian giants needed a dramatic equaliser followed by a perfect spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive Trophee des Champions victory.
The European champions seemed to be coasting towards a comfortable triumph in the showdown featuring the Ligue 1 winners and the Coupe de France winners after the French winger opened the net early on.
Yet, Marseille struck twice late to take a shock lead. First, Mason Greenwood converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own goal.
In a remarkable twist of fortune, Goncalo Ramos grabbed a crucial equaliser in the dying moments to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from Matt O'Riley and Hamed Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all converted with composure for Paris Saint-Germain to complete a convincing penalty win.
The record champions PSG, who faced 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 past thirteen years.
