The new polymeric composites with azobenzene chromophores are synthesized, and the influence of the chromophore concentration on the photoelectrical effect in films of these materials are investigated. The influence of the external electric field on the absorption spectra of azopolymer films are studied. Electro-optical properties of polymeric films are determined by the re-orientation of the dipole moments of azobenzene groups photoinduced by polarized light in the electric field. The photoelectric effect grows owing to the increase of the azobenzene chromophore concentration.