The invention provides a polyvanadic oxygen cluster compound, a preparation method and application of the compound as well as a lithium ion battery comprising the compound. The polyvanadic oxygen cluster compound provided by the invention is stable in structure, has high capacity and quick charge and discharge properties and can serve as a negative electrode material to be applied to the lithium ion battery. Furthermore, the prepared lithium ion battery also has excellent theoretical capacity and excellent cycle performance. In the method disclosed by the invention, the polyvanadic oxygen cluster compound is prepared through raw material mixing and a solvothermal method, and the method is convenient in preparation and easy to operate. Moreover, the prepared polyvanadic oxygen cluster compound has the characteristics of stable structure, excellent electrical properties and the like.