Pure α-NaMnO 2 cathode materials were prepared by solid-state reaction with Mn 2 O 3 and Na 2 CO 3 at 750°C. Electrochemical properties of Na/α-NaMnO 2 battery was investigated with electrolytes as 1M NaClO 4 EC/DEC and 1M NaBF 4 TEGDME. First discharge capacity of Na/α-NaMnO 2 cell using 1M NaClO 4 EC/DEC electrolyte and 1M NaBF 4 TEGDME electrolyte was 146mAhg −1 and 136mAhg −1 discharge capacity for the first cycle at 0.2C rate and 104mAhg −1 97mAhg −1 after 20 cycles, respectively. Na/α-NaMnO 2 battery with 1M NaClO 4 EC/DEC electrolyte shows higher initial charge/discharge capacity than that using 1M NaBF 4 TEGDME because of high ionic conductivity of electrolyte and low interfacial resistance between the electrolyte and electrode. However, Na/α-NaMnO 2 battery with 1M NaBF 4 TEGDME electrolyte has better stability for the 20th cycle from coulombic efficiency result because of stability of interfacial resistance.