The layered Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Mo x ]O2 cathode materials (x =0, 0.005, 0.01, and 0.02) were prepared by a solid-state pyrolysis method (700, 800, 850, and 900°C). Its structure and electrochemical properties were characterized by XRD, SEM, XPS, cyclic voltammetry, and charge/discharge tests. It can be learned that the doped sample of x =0.01 calcined at 800°C shows the highest first discharge capacity of 221.6mAhg−1 at a current density of 20mAg−1 in the voltage range of 2.3–4.6V, and the Mo-doped samples exhibit higher discharge capacity and better cycle-ability than the undoped one at room temperature.