Liquid nitrogen was used as a coolant in the freeze-drying method to synthesize nano-Li3V2(PO4)3/reduced graphene oxide (LVPGN) for the first time. In this material, reduced graphene oxide (rGO) (6.6 wt% in content) formed a 3D-framework and Li3V2(PO4)3 nanoparticles (30–150 nm) were strongly adhered to the surface of the rGO and enwrapped into the rGO sheets uniformly. The LVP nanoparticles can decrease the lithium ion diffusion length and the rGO can effectively improve the electronic conductivity. The material shows great rate performance with a capacity of 105.7 mAh g−1 at 20C for 3.0–4.3 V, and a good cycling performance with a discharge capacity of 123.2 mAh g−1 (96.7% of the first discharge capacity 127.4 mAh g−1) after 100 cycles at 0.1C.