The invention discloses a three-dimensional hollow titanium dioxide assembled from (001) surfaces, and a preparation method and application thereof. The three-dimensional hollow titanium dioxide can be applied to the field of manufacturing of positive electrode materials of lithium batteries. According to the invention, a hydro-thermal method is employed for preparation of titanium dioxide, and under the co-action of hydrofluoric acid and hydrogen peroxide, the hydrolysis process of a reaction intermediate peroxotitanic acid is effectively regulated and controlled. The formation process of a hollow structure is related to an Ostwald ripening mechanism, fluoride ions promote preferential growth of a crystal along [001] direction, and finally, the three-dimensional hollow product is formed. The method has the advantages of low cost, simple and controllable process, mild reaction, obtainment of the pure product and a high exposure rate of the (001) surfaces; and the titanium dioxide material prepared by using the method has the high-exposure (001) surfaces, is of a hollow micro-nano structure, can be applied to preparation of positive pole pieces of the lithium battery, shortens a diffusion path of lithium ions, facilitates intercalation/deintercalation behavior of lithium ions and alleviates volume expansion of the material during charging and discharging, and thus, the lithium battery has improved charging and discharging efficiency and prolonged cycle life.