Lithium-rich nickel–manganese–cobalt oxide, Li1.2Ni0.18Mn0.59Co0.03O2, prepared by spray-dry process, exhibits rapid capacity fade and poor rate capability. The surface of Li1.2Ni0.18Mn0.59Co0.03O2 can be modified with LiCoPO4 through co-precipitation method in order to improve its electrochemical properties. The resultant LiCoPO4 particles are in nano-scale and accumulate on the surface of the Li1.2Ni0.18Mn0.59Co0.03O2 particles. The surface modification by LiCoPO4 is shown to significantly improve both the cyclic performance and the rate capability of Li1.2Ni0.18Mn0.59Co0.03O2.