Sodium vanadate (Na₅V₁₂O₃₂ or Na_1.25V₃O₈) nanowire arrays were successfully prepared using a facile hydrothermal method with subsequent calcination. The length of the Na₅V₁₂O₃₂ nanowire arrays on titanium foil were about 10.5 μm. The unique architecture renders a high-rate transportation of lithium ions that is attributed to their nanosized structure, active materials connected to the current collector and the high specific surface area. The Na₅V₁₂O₃₂ nanowire arrays on titanium foil annealed at 250 °C as electrodes for lithium-ion batteries exhibit a significant capacity stability with a capacity from 339.3 to 289.7 mA h g⁻¹ in 50 cycles at 50 mA g⁻¹. The superior electrochemical performance demonstrated that the Na₅V₁₂O₃₂ nanowire arrays are promising electrodes for secondary organic lithium-ion batteries.