Three-dimensionally ordered macroporous (3DOM) LiCoO2 was synthesized by colloidal crystal templating method using poly(methyl methacrylate) with the diameter of 232 nm as the template. The effects of roasting temperature on properties of LiCoO2 cathode materials were investigated by thermogravimetric analysis (TG-DTG), scanning electron microscope, X-ray diffraction, transmission electron microscopy, and electrochemical measurements. The results indicated that the synthesized 3DOM LiCoO2 calcined at 700 °C had better crystal framework and electrochemical properties. The 3DOM LiCoO2 samples presented higher rate capacity compared to commercial LiCoO2 with a specific discharge capacity of 151.2 mAh g−1 at a current density of 1 C, and 92 % of the specific discharge capacity was retained after 50 charge–discharge cycling.