A practical chemical synthesis of ethyl (R)-(-)-4-Cyano-3-hydroxybutyrate ((R)-CNHB) has been accomplished from (S)-3-chloro-1, 2-propanediol, which is a main by-product originating from (S, S)-Salen Co (III) catalyzed by hydrolytic kinetic resolution (HKR) of epichlorohydrin. The new synthetic approach demonstrated an efficient utilization of organic by-product for the asymmetric synthesis of the intermediate of atorvastatin.