Metal zirconium was prepared by electro-deoxidization method by using CaCl2 molten as electrolyte, sintered ZrO2 and ZrO2 doped different mole CaCO3 pallets as cathode, graphite rod as anode. The pallets were electrolyzed at 900 ℃ and 3.1 V for 8 h. It is found that the rate of electro-deoxidization reaction for ZrO2 and the current efficiency were increased, and the reaction time of Electro-deoxidization was shortened by adding CaCO3.