A three-dimensional cross-linked Ni–V₂O₅ nanomaterial with a particle size of 250–300 nm was successfully prepared in a 1-butyl-3-methylimidazole bromide ionic liquid (IL). The formation of this structure may follow the rule of dissolution–recrystallization and the ionic liquid, as both a dissolution and structure-directing agent, plays an important role in the formation of the material. After calcination of the precursor, the active material (Ni–V₂O₅–IL) was used as an anode for lithium-ion batteries. The designed anode exhibited excellent electrochemical performance with 765 mA h g⁻¹ at a current density of 0.3 A g⁻¹ after 300 cycles, which is much higher than that of a NiVO–W material prepared via a hydrothermal method (305 mA h g⁻¹). These results show the remarkable superiority of this novel electrode material synthesized in an ionic liquid.