PSG has now secured the season-opening trophy on 14 different times.
The Parisian giants needed a dramatic leveler followed by a perfect spot-kick decider to overcome Marseille in Kuwait and capture a fourth straight French Super Cup title.
The European champions seemed to be coasting towards a comfortable win in the showdown between the Ligue 1 winners and the French Cup winners after the French winger found the net in the opening stages.
However, the southern French side struck twice in the closing moments to take a surprise advantage. First, the English forward scored from the penalty spot, before the defender inadvertently directed the ball into his own net for an own goal.
In a breathtaking turn of fortune, Goncalo Ramos grabbed a crucial leveler in the dying seconds to send the contest into a penalty shootout. PSG goalkeeper Chevalier then emerged as the hero, stopping crucial attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all scored with composure for Paris Saint-Germain to seal a convincing shootout win.
The record winners PSG, who met last season's Ligue 1 runners-up Marseille after completing a domestic double, have now lifted this competition for the twelfth time in the last thirteen seasons.