The high valence and large ionic radius of Mo6+ is selected as a dopant to modify the LiNi0.6Co0.2Mn0.2O2 material through the molecular level mixed calcination method. The Mo6+ substitutes the transition metal atoms in the material proportionately, which has no influence on the original atom ratio of the transition metal, and may expand the Li+ diffusion pathways. The strong bond energy of Mo-O benefits the stability of the material. Meanwhile the electrochemical reaction of Mo6+/Mo4+ in the process of charging and discharging might increase the capacity of the material. The electrochemical impedance spectroscopy clearly demonstrates that the Mo-doping reduces the charge transfer impedance and enhances the electrochemical reaction activity of the lithium ion. When x = 0.01, the material shows an excellent cycling and rate performance. The discharge specific capacity can reach up to 208 mAh g(-1) at 0.2C under 2.8 V-4.6 V, and remains 75% of the first discharge capacity after 101 cycles, which is 10% higher than the un-doped material.