The morphologies and structures of nanostructurally assembled V2O5 doped with Ti as well as of the inverse system, V-doped TiO2, have been studied using transmission electron microscopy and Raman spectroscopy. The bulk structure of the Ti-doped vanadia particles was found to be crystallized in a rod-like shape and to have the phase composition of V2O5 with titanium atoms nonuniformly distributed over the surface. A coherent interface between supported V2O5 and TiO2 particles was found to be the main structural peculiarity of the inverse system, V-doped TiO2 (anatase). The vanadium atoms are partially exchanged for titanium atoms at the interface, which leads to a change in the bond lengths of V=O and V-O-Ti in comparison with those observed in the monolayer supported vanadia catalysts. Both materials showed good catalytic behavior in the reaction of selective reduction of NO by NH3.