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Highlights • The β-Na 0.33 V 2 O 5 nanowires were obtained by an electrodeposited-hydrothermal method. • We have synthesized β-Na 0.33 V 2 O 5 nanowire film with high tap density. • The thickness of the β-Na 0.33 V 2 O 5 nanowires is ∼10.5 μm at 5 h, 2.5 V, 90 °C. • The β-Na 0.33 V 2 O 5 @PPy maintains a capacity of 241.7 mAh g−1 after 50 circulations. Abstract A novel electrodeposited-hydrothermal method has been developed to fabricate high-density β-Na 0.33 V 2 O 5 nanowire film on a metal current collector (Ti foil). The morphology, crystal structure, and the effects of deposition voltage, temperature and time on the prepared samples were tested and presented in detail. The thickness of the β-Na 0.33 V 2 O 5 nanowire film was ∼10.5 μm under experimental conditions of 5 h time, 2.5 V voltage, and 90 °C temperature. When the β-Na 0.33 V 2 O 5 nanowire film was coated with polypyrrole and served as a cathode of lithium-ion battery, it exhibited a high reversible discharge capacity of 269.9 mAh g−1 at a current density of 50 mA g−1. By contrast, the cycling behavior of this material is proved to be much better than the bare β-Na 0.33 V 2 O 5 nanowire film. This research provides a new pathway to explore high tap density cathode materials for lithium-ion battery with enhanced electrochemical performance. [ABSTRACT FROM AUTHOR]