The safe operating voltage and low volume variation of Li3VO4 (LVO) make it an ideal anode material for lithium (Li)-ion batteries. However, the insufficient understanding of the inner storage mechanism hinders the design of LVO-based electrodes. Herein, we investigate, for the first time, the Li-ion storage activity in LVO via Cl doping. Moreover, N-doped C coating was simultaneously achieved in the Cl doping process, resulting in synergistically improved reaction kinetics. As a result, the as-prepared Cl-doped Li3VO4 coated with N-doped C (Cl-LVO@NC) electrodes deliver a discharge capacity of 884.1 mAh/g after 200 cycles at 0.2 A/g, which is the highest among all of the LVO-based electrodes. The Cl-LVO@NC electrodes also exhibit high-capacity retention of 331.1 mAh/g at 8.0 A/g and full capacity recovery after 5 periods of rate testing over 400 cycles. After 5000 cycles at 4.0 A/g, the discharge capacity can be maintained at 423.2 mAh/g, which is superior to most LVO-based electrodes. The Li-ion storage activity in LVO via Cl doping and significant improvement in the high-rate Li-ion storage reported in this work can be used as references for the design of advanced LVO-based electrodes for high-power applications.