Metallorganic polymer systems are of practical interest because they demonstrate high rates of electro- and photoinduced charge transfer in solid state. Such polymers can be considered to be perspective materials for creation of sensors, hemotronic, photo- and electrocatalytic devices. Besides, similar polymers can be used as systems for modelling natural processes including those which proceed upon the light irradiation. Previously the optimal conditions of electrochemical synthesis of polymers based on transition metal complexes with macrocyclic ligands and their electro- and photoelectrochemical properties in different supporting electrolyte solutions have been described in detail [1, 2]. Nowadays it is considered important to study the electrical and photoelectrical properties of these polymers out of the supporting electrolyte medium. Poly[Ni(Salen)] films for low-frequency dielectric spectroscopy have been synthesized on SnO2/glass carriers in 1.0 mmol⋅dm-3 [Ni(Salen)]/ 0.1 mol⋅dm-3 TBAP/CH3CN at controlled potential electrolysis (E = 1.1 V v/s Ag/AgCl electrode) for 30 min. The investigation of influence of temperature range (293-380 K) on capacity and dielectric loss tangent (tgδ) was carried out at frequency 1, 5, 10, 50 kHz. It has been established that the charge transport in poly[Ni(Salen)] out of the supporting electrolyte solution is a thermally activated process. However, termination of temperature influence causes spontaneous return to initial state as we have observed in electrolyte solution. With temperature increase the conductivity of poly[Ni(Salen)] grows the way it takes place in materials with hopping mechanism of conductivity. The calculated magnitude of activation energy (EA ) is about 0.43 eV. The obtained frequency dependence of dielectric loss has shown decrease in the capacity with the frequency growth. Hence, we can conclude that charge transfer realizes by hopping mechaism of charge carriers among localized states. Poly[Ni(Salen)] films are photoactive in both supporting electrolyte solution and solid state. They possess photoconductivity being measured in alternating current.