The two heavyweights of the French game will vie for a place in the quarter-finals when the tie is played on October 30 or 31.
Marseille have made a perfect start to their Ligue 1 campaign with six consecutive victories, while PSG also remain unbeaten, as they look to convert a summer of heavy investment in the team to a title-winning push.
Marseille have won the Coupe de la Ligue for three consecutive seasons, while PSG last claimed it in 2008.
Ligue 2 leaders Monaco's reward for knocking out Valenciennes at the Stade Louis II is another home time, with Troyes their visitors.
Monaco's fellow second-tier sides Auxerre and Arles face away trips, to Bastia and Rennes respectively.
Coupe de la Ligue draw:
Montpellier v Bordeaux
Bastia vs Auxerre
Paris St Germain vs Marseille
Monaco vs Troyes
Lille vs Toulouse
Rennes vs Arles
Nice vs Lyon
Sochaux vs St Etienne