The catalytic effect of salts on formation of ${alpha}$-calcium sulfate hemihydrate under water vapor at atmospheric pressure was studied and the formation of q-calcium sulfate hemilydrate from by-product gypsum of phosphoric acid process was investigated. The order of catalytic effect of salts are as follow: Ammonium chloride>Sodium succinate>Calcium chloride>Sodium tartrate>Magnesium chloride The prismatic crystals was formed when ammonium chloride, calcium chloride and magnesium chloride was added, whereas the needle crystals was formed when sodium tartrate was added. Ammonium chlorideis most successful in catalytic effects in formation of ${alpha}$-calcium sulfate hermihydrate for the by-product gypsum of phosphoric acid process.