Ni-rich cathode materials LiNixCoyMn1-x-yO2 (x ≥ 0.6) have attracted much attention due to their high capacity and low cost. However, they usually suffer from rapid capacity decay and short cycle life due to their surface/interface instability, accompanied by the high Ni content. In this work, with the Ni0.9Co0.05Mn0.05(OH)2 precursor serving as a coating target, a Li-ion conductor Li2SiO3 layer was uniformly coated on Ni-rich cathode material LiNi0.9Co0.05Mn0.05O2 by a precoating and syn-lithiation method. The uniform Li2SiO3 coating layer not only improves the Li-ion diffusion kinetics of the electrode but also reduces mechanical microstrain and stabilizes the surface chemistry and structure with a strong Si-O covalent bond. These results will provide further in-depth understanding on the surface chemistry and structure stabilization mechanisms of Ni-rich cathode materials and help to develop high-capacity cathode materials for next-generation high-energy-density Li-ion batteries.