We present the mechanism for the synthesis of a layered Li(Ni1/3Co1/3Mn1/3)O2 compound by a modified radiated gel method. Pure-phase Li(Ni1/3Co1/3Mn1/3)O2 material was achieved when the polymer gel was calcined at 900°C between 15 and 30h. The unit cell parameter c decreased, and a varied slightly with increased sintering time. Electrochemical characterization revealed that the optimized sample (25h) had a high initial discharge capacity of 188mAh/g (2.8–4.5V, 20mA/g), an excellent capacity retention of 90.1% after 30 cycles and a good rate performance.