Cyclic voltammogram of (C6H8N+)5[PCu(H2O)W11O39](C6H7N)·8H2O have exhibited oxidization of anilinum cations at +0.74 V (vs Ag/AgCl). The oxidation led to the formation of hybrid film of polyaniline incorporating [PCu(H2O)W11O39]5- anion nano-clusters, which is mono-substituted Keggin-type polyoxotungstophosphate anion, at a molecular level. The electrolysis of (C6H8N+)5[PCu(H2O)W11O39](C6H7N)·8H2O was carried out at a constant potential +0.8 V (vs. Ag/AgCl), and a blue-colored thin film was deposited on transparent ITO glass substrate without any electrolyte and acidic solution. It is suggested that the electropolymerization of the anilinium cations provided the facile fabrication method of the hybrid thin film polyaniline/polyoxotungstate which consisted of conductive polymer and inorganic nano-cluster. The film was characterized by scanning electron microscope (SEM) and dynamic force microscope (DFM). The obtained images revealed the film consisted of nano-particles. The comparison of diffusion reflectance IR spectrum (DRIR) of the film with IR spectrum of (C6H8N+)5[PCu(H2O)W11O39](C6H7N)·8H2O demonstrated the existence of [PCu(H2O)W11O39]5- anion in the film. UV-vis spectra indicated that the electrolysis led to the formation of the hybrid film that includes [PCu(H2O)W11O39]5- anion in accompanying with oxidation of the polyaniline from the emerarldine salt-form to the pemigranilline-form during the electorodeposition.