Na3V2(PO4)(3) nanograins dispersed in different carbon matrices are rationally synthesized and systematically characterized. The acetylene carbon matrix provides the best conductive networks for electrons and sodium ions, which endows Na3V2(PO4)(3) stable cyclability and high rate performance. The Na3V2(PO4)(3)-based symmetric sodium-ion batteries show outstanding electrochemical performance, which is promising for large-scale and low-cost energy storage applications.