The researches of behaviour of electrochemical systems organized by a method of direct contact of the Li-anode and a polymeric composite, including co-polymer polyacrylonitrile and organic semiconductor representing salt of thiopyrily with ClO₄^- and SnCl₆^2- anions are carried out. The basic electrochemical parameters of researched systems are determined. By methods inversion voltamperometry and chronopo- tentiometiy is established, that the behaviour of such systems is defined both boundary effects, and volumetric properties of a polymeric composite. It is revealed, that the volumetric properties last are defined by thopochemical reactions. Their constants are determined. The methods of the phase x-ray and element analyses determine products of cathode restoration having properties solid-state electrolyte.