LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode material suffers from phase transformation and electrochemical performance degradation as its main drawbacks, which are strongly dependent on the surface state of NCM523. Herein, an effective surface modification approach was demonstrated; namely, the fast lithium-ion conductor (Li2O-B2O3-LiBr) was coated on NCM523. The Li2O-B2O3-LiBr coating layer as a protecting shell can prevent NCM523 particles from corrosion by the acidic electrolyte, leading to a superior discharge capacity, rate capability, and cycling stability. At room temperature, the Li2O-B2O3-LiBr-coated NCM523 exhibited an excellent capacity retention of 87.7% after 100 cycles at the rate of 1 C, which is remarkably better than that (29.8%) without the uncoated layer. Furthermore, the coating layer also increased the discharge capacity of NCM523 cathode material from 68.7 to 117.0 mAh g(-1) at 5 C. Those can be attributed to the reduction in the electrode polarization and improvement in the electrode conductivity, which was supported by electrochemical impedance spectroscopy and cyclic voltammetry measurements.