We report here the integration of high voltage Li3V2(PO4)3/C cathode material and nitrogen-doped graphene nanosheets, which has led to high-speed electron and Li-ion transfer channels. The hybrid materials are synthesized through a microwave-assisted hydrothermal method. The Li3V2(PO4)3/C with typical size of 50–100nm are uniformly anchored on the nitrogen-doped graphene nanosheets. The hybrid nanocomposites as cathode material for lithium-ion batteries exhibit a specific discharge capacity of 191.5mAhg−1 at 0.1C within the voltage range of 3.0–4.8V; 172.6mAhg−1 and 160.5mAhg−1 at higher rates of 5C and 10C, respectively. More importantly, it shows a stable cycling performance with 87.3% capacity retention after 1000 cycles at 20C. Thus, we can speculate that the nitrogen-doped graphene decorated Li3V2(PO4)3/C is a promising cathode material for use in high-rate and ultralong cycle-life lithium-ion batteries. Meanwhile, this synthesis strategy and design conception for Li3V2(PO4)3 could be employed to develop other cathode or anode materials for advanced energy storage.