Co-B alloys were synthesized via a chemical reduction method, and adopted as anode materials for alkaline secondary batteries. The structural evolutions and the electrochemical behaviors of the as-prepared Co-B alloys with increasing heat-treating temperatures were analyzed with X-ray diffraction (XRD), scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and charge-discharge test. It is found that the Co-B alloys treated at various temperatures show high reversibility. And the electrochemical activities were found to be dependent on the structural evolutions of the Co-B alloys. The amorphous Co-B alloy treated at 50 degrees C achieves an excellent discharge capacity of 304 mAh/g in the first cycle, while the Co-B alloy treated at 50 degrees C shows superior cyclicity. (C) 2008 Elsevier Ltd. All rights reserved.