Na-ion batteries are potential alternative to Li-ion batteries due to their low cost and abundance of sodium source. And Na3V2(PO4)3 is regarded as the most promising cathode material because of their high capacity and larger interstitial channels for fast Na ion migration. However, the disadvantage of low conductivity suppresses its practical applications. To increase electrochemical properties of the cathode, reduced graphene oxide-supported Na3V2(PO4)3/C (NVP/C-G) composite has been prepared, in which the graphene is used to accelerate movement of the electronics and Na ions. XRD characterizations show that the synthesized material is well corresponding to NASICON structure, and SEM image show that the graphene sheets are uniformly dispersed on surface of the composite. The initial capacity of the material is up to 103.5 mAh g−1 at 0.1 C, and 92.3 % and 92.1 % of capacities are maintained with discharge ratios of 0.5 C and 2 C over 500 cycles, proving a much better cycling stability compared with the Na3V2(PO4)3/C (NVP/C) particles. The enhanced discharge capacities and retention rate of the NVP/C-G could be ascribed to the tight contact between NVP/C and RGO sheets, which is beneficial to fast electron transport and better intercalation/deintercalation of Na+ through the nanoparticles. Therefore, the synthesized NVP/C-G displays highly potential for practical use in sodium-ion batteries.