Application of a redox polymer of the poly-[Me(R-Salen)] type onto a conducting substrate is accomplished by the method of electrochemical polymerization. Said polymerization is accomplished by supplying a voltage between the substrate (that serves as an anode) and a counter electrode (that serves as a cathode), with both of them being submerged into the electrolyte containing an organic solvent and the compounds capable of dissolving in said solvent. The process is accompanied by the production of electrochemically inactive (at concentrations of no less than 0.01 mol/l) ions within the range of potentials from -3.0 V to +1.5 V, and metal complex [Me(R-Salen)] dissolved at a concentration of no less than 5-10.sup.-5 mol/l, (where: Me is a transition metal having at least two different degrees of oxidation, R is an electron-donating substituent, Salen is a residue of bis-(salicylaldehyde)-ethylenediamine in Schiff's base.