MgO-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 was synthesized via melting impregnation method followed by a solid state reaction. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) show that the MgO layer is well coated on the surface of the layered oxide particles. Although the initial discharge capacity of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 with proper MgO modification decreases compared to the bare one, the 2wt.% MgO coated cathode exhibits the excellent cycling stability with capacity retention of 96.4% at a current density of 200mAg−1 after 100 cycles at room temperature and 94.3% after 50 cycles at 60°C. Electrochemical impedance spectroscopy (EIS) shows that the thin MgO layer mainly reduces the charge transfer resistance and stabilizes the surface structure of active material during cycling. Melting impregnation method is promising for MgO coating to improving the cycling stability of Li-rich layered oxide cathode for Li-ion batteries.