Engineering the exposed surface of primary particles is a viable strategy to enhance the charging rate and structural stability of high-voltage LiN0.5C0.2M0.3O2 (NCM) cathode materials. Herein, we have developed highly conductive Na2MoO4 and engineered the exposed surface of NCM by a simple infiltration and subsequent low-temperature melting process. Such an ingenious strategy can achieve a high-quality and uniform coating layer for effectively decreasing the side effects between electrode materials and the electrolyte with a rapid electron transfer pathway network. Consequently, the as-obtained NCM-NMO delivers improved reversible capacities of 202.5 mAh g(-1) at 0.2C and 129.0 mAh g(-1) at 10C in 3.0-4.5 V, which is much higher than the unmodified NCM (86.1 mAh g(-1)@10C). After 100 cycles at 1C, 91% reversible capacity is retained with a negligible voltage plateau and structural change. This finding demonstrates a novel concept to modify the primary particles of cathode materials by engineering their exposed surface.