α-Muricholic acid was synthesized from hyodeoxycholic acid via esterification, selective oxidation, hy-droxylation of C-7 methylene, carbonyl reduction at C-6 and hydrolysis reactions. The resulting product was finally confirmed by 1H-NMR, 13C-NMR and HRMS. The overall yield from hyodeoxycholic acid was calculated to be 28.9±0.3%. The effect of catalysts on the yield of intermediateⅡand the process stability of the esterification reaction was investigated. The oxidants on the selective oxidation of C-3 or C-6 hy-droxyl group in intermediate Ⅱ were screened, and 2-iodobenzoic acid (IBX) was approved to be good candidate in selective oxidation of the C-6 hydroxyl group in intermediate Ⅱ. The effects of the molecu-lar ratio of Ⅱ to IBX on the yield of intermediate Ⅲ and the process stability under the conditions were explored, and the results were as follow: 1) the yield of intermediate Ⅱ was 99.0% by using concentrated HCl as the catalyst; 2) IBX could selectively oxidize hydroxyl group at C-6 of intermediate Ⅱ and the yield of the intermediate Ⅲ was 82.3% when the ratio of n (Ⅱ): n (IBX) was 1: 1.20; 3) the single crystal structure of intermediate Ⅲ was determined, and its absolute configuration was as expected.