PSG has now claimed the prestigious trophy on fourteen separate times.
The Parisian giants needed a dramatic equaliser followed by a successful spot-kick decider to overcome Marseille in the Gulf and capture a record-extending fourth consecutive French Super Cup victory.
The European champions seemed to be sailing towards a comfortable triumph in the match featuring the French league winners and the Coupe de France holders after the French winger found the scoring early on.
Yet, the southern French side fired twice late to take a surprise advantage. Initially, Mason Greenwood converted from the spot-kick, before the defender inadvertently directed the ball into his own net for an own goal.
In a remarkable twist of fortune, the Portuguese striker grabbed a vital equaliser in the final seconds to force the contest into a deciding shootout. The Parisian shot-stopper Lucas Chevalier then emerged as the key figure, stopping crucial kicks from O'Riley and Traore.
In the shootout, Goncalo Ramos, Vitinha, the full-back, and the young talent all scored with composure for PSG to complete a 4-1 shootout victory.
The record champions PSG, who met last season's Ligue 1 second-placed team Marseille after completing a league and cup double, have now lifted this competition for the twelfth time in the past thirteen years.
