A series of Co x B (x =1, 2, 3) alloys were prepared by arc melting, the phase structure of the alloys were characterized by X-ray diffraction (XRD). The electrochemical experimental results demonstrated that the Co x B (x =1, 2, 3) series alloys showed excellent cycling stability, the capacity retention was 94.2%, 93.6% and 93.8% in the 100th cycle, respectively, as the cobalt content decreased. The CoB alloy electrode showed very good electrochemical reversibility in cyclic voltammetry (CV) curves, the oxidation and reduction peaks resembled the pure cobalt element powder electrode. The electrode mechanism was discussed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), using pure CoB alloy cast electrode. From the SEM, after first and second cycle, the surface became porous and pulverous; also, the oxidation state of Co changed through XPS, after second cycle, the Co of 0 oxidation state could not be found on the surface. Based on the experiment, a proper mechanism was proposed: on this condition, the discharge capacity may due to the Co(OH)2/Co reaction, which happened on the porous surface as the boron dissolved when the cycle increased.