Li0.33MnO2 cathode material was synthesized by solid state reaction. The material showed a small coherent domain size about 10 nm determined by X-ray diffraction and transmission electron microscopy. The electrochemical properties of the material were studied in different potential windows of 3.5―2.0 V and 4.3―2.0 V. An irreversible transformation to spinel phase was observed in the initial several cycles, which was more prominent on cycling at 4.3―2.0 V. Electrochemical impedance spectroscopy showed that the Li+ diffusion coefficient of the material was about 2×10–9 cm2/s. Li0.33MnO2 showed a reversible discharge capacity of 140 and 200 mA·h/g in the potential windows of 3.5―2.0 V and 4.3―2.0 V, respectively. But the capacity retention at 4.3―2.0 V was poor due to the thicker spinel layer formed on the material surface. Li0.33MnO2 cathode material was synthesized by solid state reaction. The material showed a small coherent domain size about 10 nm determined by X-ray diffraction and transmission electron microscopy. The electrochemical properties of the material were studied in different potential windows of 3.5-2.0 V and 4.3-2.0 V. An irreversible transformation to spinel phase was observed in the initial several cycles, which was more prominent on cycling at 4.3-2.0 V. Electrochemical impedance spectroscopy showed that the Li + diffusion coefficient of the material was about 2 × 10 -9 cm2 / s. Li0.33MnO2 showed a reversible discharge capacity of 140 and 200 mA · h / g in the potential windows of 3.5-2.0 V and 4.3-2.0 V, respectively. But the capacity retention at 4.3-2.0 V was poor due to the thicker spinel layer formed on the material surface.