Calcium zincate as an active material in Zn/Ni secondary battery has been successfully synthesized by microwave method. The chemical composition of Ca(OH)2·2Zn(OH)2·2H2O was confirmed by X-ray powder diffraction pattern and weight loss in thermogravimetric analysis.The results of cyclic voltammetry and experimental Zn/Ni battery charge–discharge test showed that the material of calcium zincate had excellent electrochemical performances: a high discharging platform of 1.685 V and a good cycleability, discharge capacity would be 70.0% of initial capacity after circulated 120 times.