A series of Li[Cr x Li(1−x)/3Mn2(1−x)/3]O2 (0.15≤ x ≤0.3) cathode materials was prepared by citric acid-assisted, sol–gel process. Sub-micron sized particles were obtained and the X-ray diffraction (XRD) results showed that the crystal structure was similar to layered lithium transition metal oxides (R-3m space group). The electrochemical performance of the cathodes was evaluated over the voltage range 2.0–4.9V at a current density of 7.947mAg−1. The Li1.27Cr0.2Mn0.53O2 electrode delivered a high reversible capacity of up to 280mAhg−1 during cycling. Li[Cr x Li(1−x)/3Mn2(1−x)/3]O2 yielded a promising cathode material.