Abstract: This research makes an exploitation on the law of chloridizing volatilization of gallium during vanadium slag roasting with single addition of NaCl and with simultaneous addition of Na₂CO₃ and NaCl in a temperature range of 200~1000℃.When NaCl is solely added to vanadium slag for mixed roasting.the volatilization rate of gallium (η_Ga) increases with the amount of NaCl added,however the trend is not obvious and the conversion rate from vanadium to aqueous sodium vanadate remains low,when Na₂CO₃ and NaCl are added simultaneously to vanadium slag for mixed roasting.the effect is satisfactory.With the burden ratio of W_(v-slag)/(W_Na2CO3+W_NaCl)=8/2,W_Na2CO3/W_NaCl=2,one hour roasting at 800℃ would result in vanadium conversion rate of 85% and η_Ga of 30%.Besides.η_Ga increase with rise of the roasting temperature.However,to ensure the conversion of vanadium,it is reasonable to control the roasting temperature between 800~900℃.