The Parisian club has now won the season-opening trophy on 14 separate times.
Paris Saint-Germain needed a dramatic leveler followed by a perfect penalty shootout to get past Marseille in Kuwait and capture a fourth straight French Super Cup victory.
The European champions seemed to be sailing towards a straightforward triumph in the match between the Ligue 1 winners and the Coupe de France winners after Ousmane Dembele found the net in the opening stages.
However, Marseille struck twice in the closing moments to take a surprise lead. First, the English forward scored from the penalty spot, before the defender unfortunately turned the ball into his own net for an own-goal.
In a remarkable twist of events, Goncalo Ramos snatched a crucial equaliser in the dying seconds to send the match into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the hero, stopping decisive kicks from O'Riley and Traore.
From the spot, Goncalo Ramos, the midfielder, Nuno Mendes, and Desire Doue all converted successfully for PSG to seal a convincing shootout victory.
The record winners Paris Saint-Germain, who faced last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last 13 years.
