The NaFe0.95V0.05PO4/C composite is synthesized by electrochemical ion displacement from LiFe0.95V0.05PO4/C composite in aqueous NaNO3 solution. A coulombic capacity amounting to ∼105 and ∼82 mAh g−1 at sodiation/desodiation rate of 500 and 5000 mAg−1, respectively, is evidenced. For the sake of comparison the same investigations is performed with LiFe0.95V0.05PO4/C composite in LiNO3 solution, and better capacity retention and rate performance is evidenced for NaFe0.95V0.05PO4/C one. This advancement is found to be due a higher participation of pseudocapacity in the sodiation/desodiation charge storage process. An aqueous battery composed of NaFe0.95V0.05PO4/C cathode, belt-like Na1.2V3O8 anode and NaNO3 solution as an electrolyte, tested galvanostatically, displays long-life performance with only 10% of capacity fade after 1000 charge/discharge cycles.