PSG has now claimed the season-opening cup on 14 separate times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome their arch-rivals in the Gulf and secure a fourth straight Trophee des Champions victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the Ligue 1 winners and the French Cup holders after the French winger opened the net in the opening stages.
However, the southern French side struck twice late to seize a surprise advantage. Initially, the English forward converted from the spot-kick, before the defender unfortunately turned the ball into his own net for an own goal.
In a remarkable turn of fortune, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a penalty shootout. PSG goalkeeper Chevalier then emerged as the key figure, saving crucial kicks from O'Riley and Hamed Traore.
In the shootout, Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout win.
The record winners Paris Saint-Germain, who met last season's Ligue 1 second-placed team Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last 13 years.
