A simple wet chemical process followed by high temperature calcination has been successfully used to coat Li-ion conductive Li4Ti5O12 on the surface of Ni-rich LiNi0.8Co0.1Mn0.1O2. Physicochemical characterization results indicate that a Li4Ti5O12 with a thickness of about 2–3 nm was uniformly distributed on the surface of microspheres, without inducing significant change of the structure and morphology. Electrochemical test results show that proper content of Li4Ti5O12 coating layer can greatly improve the cycling performance and rate capability of Ni-rich LiNi0.8Co0.1Mn0.1O2 for the improved Li+ ions diffusion rate and suppressed side reactions between electrode and electrolyte. Notably, the 1 wt% Li4Ti5O12 coated sample exhibits excellent cycling stability with the capacity retention of 75.86% at 1 C after 170 cycles when cycled between 2.7 and 4.3 V at 25 °C, while that is only 39.40% for bare LiNi0.8Co0.1Mn0.1O2.