NaBiO3 crystal of high purity has been synthesized through chemical oxidization. The morphology and thermal stability of NaBiO3 were examined with scanning electron microscope (SEM) and thermogravimetry-differential scanning calorimetry (TG-DSC). The electrochemical properties of MnO2 electrodes with and without doping NaBiO3 were studied through galvanostatic charge/discharge and cyclic voltammetry. The results indicate that the MnO2 electrode doped with NaBiO3 possesses remarkably higher discharge voltage and capacity and better reversibility than the pure MnO2 electrode and Bi2O3 doping MnO2 electrode.