A series of cathode materials with molecular notation of xLi[Li1/3Mn2/3]O2·(1− x)Li[Ni1/3Mn1/3Co1/3]O2 (0≤ x ≤0.9) were synthesized by combination of co-precipitation and solid state calcination method. The prepared materials were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques, and their electrochemical performances were investigated. The results showed that sample 0.6Li[Li1/3Mn2/3]O2·0.4Li[Ni1/3Mn1/3Co1/3]O2 (x =0.6) delivers the highest capacity and shows good capacity-retention, which delivers a capacity ∼250mAhg−1 between 2.0 and 4.8V at 18mAg−1.