The properties of calcium zincate as negative electrode materials for secondary batteries were examined by powder microelectrode, cyclic voltammetry, charge–discharge cycle measurements and X-ray diffraction (XRD) analysis. The results show that the cycleability of calcium zincate is obviously superior to that of ZnO and that of the mixture of ZnO and Ca(OH)2 (the molar ratio of Zn:Ca=2:1). Calcium zincate forms zinc metal during the charging and exhibits an initial discharge capacity 230mAhg−1. With the discharge cut-off voltage of 1.0V, the discharge capacity of the experimental Zn/NiOOH cell does not decay much during 500 cycles, exhibiting good prospect for practical use.