The 16-dehydropregnenolone acetate oxime was a key intermediate to synthesis many steroids products, such as dehydroepiandrosterone, nandrolone decanoate, and norethisterone.The pyridine, a limited solvent because of the toxicity to operator and the environment, was used in the literature process.Through the experiment research, the sodium acetate water solution was found successfully to replace the pyridine, and the adding quantity and the reaction time have been researched.The optimal process was got using the sodium acetate to replace the pyridine, the quality ratio 0.5:1, react 1 h at 50-60 °C and then reflux for 2 h.The green synthesis was realized, and yield was increased obviously.