LiNi1/3Co1/3Mn1/3O2 (LNCM) cathode material with high specific capacity has been received extensive attention in power batteries. However, the poor cycle performance and serious safety issues limit its application prospect. In this paper, the technology of surfactant-assisted hydrothermal synthesis combined with vanadium pentoxide (V2O5) coating is applied in LNCM cathode material. Firstly, the Ni1/3Co1/3Mn1/3CO3 precursor with good dispersibility and uniform morphology is synthesized by surfactant-assisted hydrothermal reaction. Secondly, the precursor is uniformly mixed with the lithium salt and ammonium metavanadate in the solution. Experienced drying and sintering processes, the LNCM cathode material uniformly coated with V2O5 is achieved. The electrochemical test results show that the discharge specific capacity of LNCM cathode material coated with 2 wt% V2O5 reaches 101.7 mAh ·g−1 at 10 C, and the capacity retention rate has 89.12% after 100 cycles at 0.5 C. Both of the novel synthetic method and the coating effect of V2O5 reduce electrolyte side reaction on the LNCM cathode material, and accelerate Li+ diffusion rate, then further derive more desirable electrochemical properties.