PSG has now claimed the season-opening cup on 14 separate occasions.
The Parisian giants required a dramatic equaliser followed by a perfect spot-kick decider to overcome Marseille in the Gulf and secure a record-extending fourth consecutive Trophee des Champions victory.
The Champions League holders seemed to be sailing towards a straightforward win in the showdown between the Ligue 1 winners and the Coupe de France holders after the French winger opened the scoring early on.
Yet, the southern French side struck twice late to take a shock lead. First, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of events, Goncalo Ramos grabbed a vital equaliser in the dying seconds to force the contest into a deciding shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving decisive attempts from O'Riley and Hamed Traore.
From the spot, Ramos, the midfielder, the full-back, and the young talent all converted successfully for Paris Saint-Germain to seal a convincing penalty victory.
Now 14-time winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after achieving a domestic double, have now lifted this competition for the 12th time in the past 13 years.
