Claudio Ranieri's men sit top of the Ligue 1 table and are undefeated after the first five games, with star striker Radamel Falcao already finding the net on four occasions.
However, the principality club have not won a major trophy since 2003, when they beat Sochaux 4-1 in the Coupe de la Ligue final, and they will start their quest to regain the crown against a Reims side that has lost just once so far this season.
Rennes, who reached last year's final only to lose to Saint-Etienne, host Ligue 2 Nancy, while Brittany rivals Nantes and Lorient face-off at the Stade de la Beaujoire.
Bastia have been drawn against Corsican neighbours Ajaccio, Lille take on Auxerre, and 2011-12 Ligue 1 winners Montpellier travel to Sochaux.
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