Refluxing the aqueous solutions of V2O5 and mono-Valent cations, M(+) (M : Li, Na, K, Cs and NH4) and of V2O5 and di-valent cations M (M : Ca, Mn, Co, Ni and Cu) below the boiling point, vanadium xerogels, M-V2O5-H2O, were synthesized except for Cs. By drying the suspensions of these xerogels on a glass substrate, the crystallite of the xerogels were preferentially oriented in the films with their (001) planes parallel to the film surface. The formation process of the xerogels was discussed in relation to ionic radii of M(+) and M(2+).