The Li2MnO3 coated LiNi0.8Mn0.1Co0.1O2 electrode has been sucessfully synthesized through a PVP-chelation and syn-lithiation strategy. X-ray diffraction (XRD) and X-ray photoelectron Spectrometer (XPS) characterizations are applied to verify the existence of the Li2MnO3 surface layer. The complete and nanoscale Li2MnO3 coating layer strongly adheres to the host material because of the layered/layered homostyructure, improves the content of Mn element on the surface of the electrode and has three-dimensional path for Li+-ion diffusion. Due to the numerous unique and dramatic advantages of the Li2MnO3 surface layer, the layered/layered homostyructure electrode exhibits superior cycle stability, rate capability and other electrochemical properties. The newly developmental coating material and versatile nanocoating strategy can also be popularized and applied in other electrode materials.