Lithium-rich layered cathode Li1.2Mn0.54Ni0.13Co0.13O2 is synthesized by a co-precipitation method followed by high-temperature treatment and surface coated with different amount of amorphous FePO4. The microstructure and electrochemical performance of the as-prepared cathode materials are investigated systematically. It is demonstrated that the Li1.2Mn0.54Ni0.13Co0.13O2 particles are uniformly coated with amorphous FePO4. With proper amount of amorphous FePO4 coating layer, significant improvements in discharge capacity, initial Coulombic efficiency, rate capability, cycle performance, and thermal stability are achieved at room temperature. Specifically, the 3 wt.% FePO4-coated cathode exhibits the highest discharge specific capacities (271.7 mAh g−1 at C/20), improved initial Coulombic efficiency (85.1%), and best cyclability (discharge capacity of 202.6 mAh g−1 at C/2 after 100 cycles), while the 1 wt.% FePO4-coated cathode displays the best rate capability (194.3 mAh g−1 at 1 C rate and 167.9 mAh g−1 at 2 C rate). The charge–discharge curves and electrochemical impedance spectra reveal that the improved electrochemical performances are due to the suppression of both the oxygen vacancy elimination at the end of the first charge and side reactions of the cathode with the electrolyte, as well as the decrease in charge transfer polarization by the FePO4 coating layer.