Poly-zinc-octaethylporphyrin/P5W30 films have been obtained through incorporation of Preyssler-type polyoxometalate ions, namely [NaP5W30O110] 14-(P5W30) into zinc octaethylporphyrin/viologen-based polymers (poly-ZnOEP) films. The latter has been achieved through a metathesis reaction involving exchange of the initial counter ions (PF6-) of the positively charged poly-ZnOEP by P5W30. The investigated polymers involve ZnOEP units covalently linked through either dicationic mono-viologen or through tetracationic bis-viologen spacers. These copolymers have been characterized by UV/Vis spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, AFM and by electrochemical impedance spectroscopy. Formation of the polymers through electropolymerization of viologen and porphyrin building blocks was monitored by EQCM. QCM was also used to study the exchange of PF6-by [NaP5W30O110] 14-. The photovoltaic performances under visible light irradiation have also been investigated by photocurrent transient measurements carried out under visible illumination.