5-Androstene-3β-ol-17-one-3-acetate is a key intermediate to synthesize many steroids products, such as dehydroepiandrosterone, nandrolone decanoate, estradiol, norethisterone of androgen, estrogen and progesterone.Based on the experiment research, the best process was using hydrochloric acid to replace phosphorus oxychloride.As a reaction catalyst, the quality ratio of added hydrochloric acid and material I was 0.5:1.Toluene and acetone are found successfully to replace benzene, and the quality ratio of added toluene and acetone and material I was 2.5:2.5:1.We improved to achieve green synthesis, and increased yield.