This paper introduced a method for synthesis of 5-hydroxy-15β, 16β-methylene-3β-pivaloyloxy-5β-androst-6-en-17-one, the key intermediate of drospirenone, with the starting material of 5, 6 β-epoxy-7β-hydroxy-15β, 16β-methylene-3β-pivaloyloxy-5β-androst-17-one being introduced via process of sulfonylation, bromination, ring opening and debromination. The reaction conditions of sulfonylation, bromination, ring opening and debromination were optimized, and the total yield was increased to 66.8%. The method was simple to operate and the structure of the product was confirmed by ∼1 HNMR, ∼(13)CNMR and ESI-MS.