In comparison with the chemical hydration and hydrolysis of nitriles, which usually involves harsh reaction conditions and low selectivity, biocatalytic desymmetrizations of prochiral or meso nitriles are highly efficient, highly enantioselective and environmentally benign.Therefore, biocatalysis and biotransformation has offered an attractive and unique protocol for the enantioselective synthesis of polyfunctionalized organic compounds that are not readily obtainable by other methods.This review summarizes the biocatalytic desymmetrization of prochiral nitriles including glutaronitriles, malonitriles and meso cyclic dinitriles during the past two decades.