MoO3-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode materials were synthesized via using co-precipitation method and wet coating process, and their crystal structure and particle morphology were analyzed and observed by XRD, SEM and TEM. The electrochemical properties of these materials were investigated and analyzed by using charge-discharge tests and electrochemical impedance spectroscopy. The results showed that the surface coating on Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode was composed of α-MoO3 and Li2MoO4, and the electrochemical properties were improved after coated with MoO3 thin films. The initial coulombic efficiencies increased from 71.2% to 79.3% when the MoO3 content increased to 5wt.%. Particularly, the 3wt.% MoO3-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 showed the highest capacity retention of 90.8% after 100 cycles, and possessed the excellent rate discharge performance. The electrochemical impedance spectroscopy (EIS) and cyclic voltammetric results demonstrated that the layered MoO3 coating could restrain the increment of the charge transfer resistance and stabilize the active material structure during cyclic process.