PSG has now claimed the season-opening cup on 14 different times.
The Parisian giants required a stoppage-time equaliser followed by a successful spot-kick decider to get past Marseille in Kuwait and capture a record-extending fourth consecutive French Super Cup victory.
The European champions appeared to be sailing towards a straightforward triumph in the match featuring the French league winners and the Coupe de France holders after the French winger opened the net early on.
However, Marseille fired twice in the closing moments to seize a shock lead. First, the English forward converted from the penalty spot, before Willian Pacho unfortunately directed the ball into his own net for an own-goal.
In a remarkable turn of events, the Portuguese striker snatched a vital leveler in the final moments to send the contest into a penalty shootout. The Parisian shot-stopper Chevalier then stood as the hero, stopping decisive attempts from O'Riley and Hamed Traore.
From the spot, Goncalo Ramos, Vitinha, the full-back, and Desire Doue all converted 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 Olympique de Marseille after completing a league and cup double, have now lifted this competition for the 12th time in the last 13 seasons.
