Herein, we reported a facile method to synthesize the nanostructured vanadium oxides by electrochemical deposition, followed by thermal treatment. Polymer surfactant was selected as a template agent to control the nanostructures. Nanorod-, nanoparticle- and platelet-structured vanadium oxides with different sizes were obtained by simply changing the surfactant concentrations. The crystallinity of various nanostructured vanadium oxide was confirmed by X-ray diffraction. X-ray photoelectron spectroscopic analysis reveals a mixed valence nature of vanadium specie in which the amount of V(V) and V(IV) species is not significantly affected by varying the surfactant concentrations. Cyclic-voltammetry curves show that the smallest potential separation between the cathodic and anodic peaks for the nanorod-structured vanadium oxide. The nanorod-structured vanadium oxide exhibits excellent Li-ion intercalation properties, much better than that of the nanoparticle- and platelet-structured vanadium oxides. Thus, the excellent performance with low-cost make the nanorod-structured vanadium oxide promising potential as a cathode material for the Li-ion battery applications.