The present invention relates to a hexagonal vanadium pentoxide nano-material as well as a preparation method and an application thereof. The vanadium pentoxide nano-material is hexagonal, and the thickness of each angle is about 100-300 nm. The preparation method comprises the following steps: using vanadium pentoxide powder, benzyl alcohol, and isopropanol as raw materials, preparing vanadium oxide collosol through reflux condensation and distillation concentration, mixing the collosol, ethanol and deionized water to obtain a vanadium pentoxide nano-material through a hydrothermal reaction and post sintering treatment. The prepared vanadium pentoxide nano-material is extremely suitable for an anode material of lithium-ion batteries. Compared with the prior art, the nano-material has the advantages of simple process, low manufacturing costs and excellent electrochemical performance and the like.