Low selectivity for lincomycin in butanol extraction process leads to relatively higher content of impurities. A novel process for extraction of lincomycin from fermentation broth was studied in this work. Mixture of n-octanol and n-decanol is used as extractant to replace n-butanol in extraction of lincomycin. Optimal operation conditions for the process have been studied. Due to higher extraction selectivity for lincomycin A by long-chain alcohol, content of impurity (lincomycin B) in the final product is much lower than that in product by butanol process. Furthermore, the practicability for combination of long-chain alcohol and butanol in purification of lincomycin was investigated.