The desymmetrization of meso-diamines was accomplished via enantioselective monobenzoylation facilitated by the cooperative action of two small-molecule catalysts. A chiral acyl-transfer reagent is formed in situ through the interplay of benzoic anhydride, 4-(dimethylamino)pyridine as a nucleophilic catalyst, and a chiral amide-thiourea cocatalyst.