Li3VO4-coated Li[Ni0.5Co0.2Mn0.3]O2 cathode material exhibits much better cycling stability, rate capability, and high voltage cycling behavior than pristine Li[Ni0.5Co0.2Mn0.3]O2 at room temperature. The sample coated with 3 wt.% Li3VO4 shows the optimum electrochemical performance. It delivers a capacity of 61.5 mAh g−1 at 10 C (1800 mA g−1) after 100 cycles. The capacity retention at 1 C (180 mA g−1) is 63.5% at cut-off voltage 4.6 V, and 63.0% at a higher cut-off voltage 4.8 V. XRD and XPS results reveal that the Li3VO4 coating layer reinforces the surface of matrix material, which benefits structural stability of Li[Ni0.5Co0.2Mn0.3]O2 during long-term cycling. CV and EIS tests indicate that the improvement of electrochemical performances could be attributed to higher Li+ conductivity, suppression of Co and Mn dissolution from Li[Ni0.5Co0.2Mn0.3]O2, and decreased polarization during cycling since Li3VO4 layer on Li[Ni0.5Co0.2Mn0.3]O2 surface acts as a relatively stable protective barrier as well as an excellent Li-ion conductor.