Submicron-sized LiNi1/3Co1/3Mn1/3O2 cathode materials were synthesized using a simple self-propagating solid-state metathesis method with the help of ball milling and the following calcination. A mixture of Li(ac)·2H2O, Ni(ac)2·4H2O, Co(ac)2·4H2O, Mn(ac)2·4H2O (ac=acetate) and excess H2C2O4·2H2O was used as starting material without any solvent. XRD analyses indicate that the LiNi1/3Co1/3Mn1/3O2 materials were formed with typical hexagonal structure. The FESEM images show that the primary particle size of the LiNi1/3Co1/3Mn1/3O2 materials gradually increases from about 100nm at 700°C to 200–500nm at 950°C with increasing calcination temperature. Among the synthesized materials, the LiNi1/3Co1/3Mn1/3O2 material calcined at 900°C exhibits excellent electrochemical performance. The steady discharge capacities of the material cycled at 1C (160mAg−1) rate are at about 140mAhg−1 after 100cycles in the voltage range 3–4.5V (versus Li+/Li) and the capacity retention is about 87% at the 350th cycle.