The electrochemical properties of microwave-synthesized LiCoO2 have been investigated by galvanostatic intermittent titration technique (GITT), impedance spectroscopic analysis (EIS) and charge/discharge capacity measurement. The results of EIS indicate that the cathode composed of microwave-synthesized LiCoO2 has large cathode/electrolyte interface area due to its fine powder size, which leads to good cyclability and capability to withstand large current density.