Li2SiO3-coated LiNi0.6Co0.2Mn0.2O2 cathode material has been synthesized and exhibit much better electrochemical performance than pristine LiNi0.6Co0.2Mn0.2O2 at cut-off voltage 4.6V. The as-prepared samples are characterized by X-ray diffraction, field emission scanning electron microscopy, field emission transmission electron microscope, and X-ray photoelectron spectroscopic. The results show that the coating-layer Li2SiO3 is not incorporated into the LiNi0.6Co0.2Mn0.2O2 host structure and coated well on the surface of the active material. The sample coated with 3mol. % Li2SiO3 delivers a capacity of 168mAhg−1 at 0.2C after 100 cycles, and remains 85.5% of the first discharge capacity. The capacity retention at 1C is 73.6% after 100 cycles and the first discharge capacity reaches 158mAhg−1 at 10C. This superior performance is attributed to the coating layer which restrains the side reactions at electrode/electrolyte interface and enhances structure stability, meanwhile, it can decrease the electrode polarization because it is an excellent Li+-ion conductor.