Anode materials with long cycling life and rate capability have remained a great challenge for sodium-ion batteries. Herein, a vanadium-based orthophosphate, NaV3(PO4)3/C nanocomposite has been investigated as a novel anode material for Na-ion batteries. The electrochemical performance of NaV3(PO4)3/C nanocomposite is evaluated in Na-half cell, which delivers a reversible capacity of 146mAhg−1 at the charging/discharging rate of 1C, and remarkable rate capability. EIS, XPS and in-situ XRD are performed to give the insight into interfacial property of electrode and structural evolution of material during cycling. The excellent cycling stability could be attributed to stable interface at higher cutoff voltage and slight change of structure with intercalation/deintercalation of Na+. Moreover, we achieve a Na-ion full battery with long term cycle life based on NaV3(PO4)3/C anode and Na3V2(PO4)3/C cathode, retaining 80% of initial capacity after 1000 cycles at charging/discharging rate of 5C, suggesting the feasibility of the as-obtained materials applied as a promising candidate for anode of Na-ion batteries.