Azopolymers and polycomplexes with cobalt based on them are synthesized, thermal behavior of the side chain polymethacrylates and their polycomplexes containing substituted azobenzene units as mesogens attached directly to the polymeric backbone and the influence of temperature on the photoelectric effect in films of these materials are investigated. The influence of the electric field on the transmission of polarized light is attributed to the appearance of forces affecting the dipole moments of photoisomers of azobenzene groups and metallic ions. The synthesized polymer materials showed a good thermal stability. The introduction of substituents of the different nature or spacers decreases the influence of metallic ions on the electro-optical properties of polycomplex films.