A new layered type lithium nickel manganese vanadium oxide with the composition of LiNi1/2Mn1/3V1/6O2 was synthesized by rheological phase reaction method. The morphology, structural and electrochemical behavior were characterized by means of SEM, X-ray diffraction analysis and electrochemical charge–discharge tests. Phase-pure LiNi1/2Mn1/3V1/6O2 was obtained when the mixed precursors of Ni–Mn–V–O composite oxide and LiOH were calcined at 800°C for 30h. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation states of Ni, Mn and V. It is found that the submicro-sized LiNi1/2Mn1/3V1/6O2 delivers an initial discharge capacity of 142mAh/g in the cut-off voltage of 2.5–4.8V, and exhibits good cycle performance.