The Parisian club has now secured the season-opening cup on fourteen separate occasions.
The Parisian giants required a stoppage-time equaliser followed by a perfect penalty shootout to get past their arch-rivals in the Gulf and capture a fourth straight Trophee des Champions title.
The Champions League holders appeared to be sailing towards a straightforward triumph in the match featuring the French league champions and the French Cup winners after the French winger opened the net early on.
However, the southern French side fired twice in the closing moments to take a shock advantage. Initially, Mason Greenwood converted from the penalty spot, before the defender unfortunately turned the ball into his own net for an own goal.
In a breathtaking twist of events, Goncalo Ramos snatched a vital equaliser in the dying seconds to send the match into a deciding shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial kicks from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and the young talent all scored with composure for PSG to complete a convincing shootout victory.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after achieving a league and cup double, have now won this competition for the twelfth time in the last thirteen seasons.
