We have prepared Ni-V(2)O(5)(.)nH(2)O core-shell nanocable arrays for Li+ intercalation applications. Ni-V(2)O(5)(.)nH(2)O nanocables were prepared via formation of Ni nanorod arrays through the template based electrochemical deposition, followed by coating of V(2)O(5)(.)nH(2)O on Ni nanorods through electrophoretic deposition. Transmission electron microscopy (TEM) micrograph clearly shows the Ni core was covered completely by a V(2)O(5)(.)nH(2)O shell. Electrochemical analysis demonstrates that in a current density of 1.6 A/g, the Li+ intercalation capacity of Ni-V(2)O(5)(.)nH(2)O nanocable array is approximately 10 times higher than that of single-crystal V2O5 nanorod array and 20 times higher than that of sol-gel-derived V2O5 film. Both energy density and power density of such nanocable-array electrodes are higher than the V2O5 film electrode by at least I order of magnitude. Such significant improvement in electrochemical performance is due to the large surface area and short diffusion path offered by the nanostructured V(2)O(5)(.)nH(2)O.