A copper complex of the half-unit 2,6-diacetylpyridine-mono(ethylenediamine) was prepared and characterized using analytical, spectral and magnetic measurements. The electropolymerization of this complex on glassy carbon electrode was performed. A new electroactive polymeric film was prepared by potential sweep electrolysis. Electroanalytical studies were carried out using the cyclic voltammetric technique to examine the indirect electroreduction of 2-aryl-4-cyano-6-mereapto-5-phenyl-3-(2H)-pyridiazinimine derivatives (compounds IIa-IId) modified with the Cu complex. In the absence of compounds IIa-IId the film showed a single pair of peaks corresponding to the Cu(II)/Cu(I) redox system. However, in the presence of the imino compounds, a catalytic effect was observed and the anodic peak for Cu(I) oxidation disappeared at low scan rates. The imino group was reduced to give the corresponding amino compounds. Direct electrochemical reduction of compounds IIa-IId was performed for comparison. The proposed mechanism has been confirmed by cyclic voltammetry and the product of controlled-potential electrolysis was identified via elemental analysis, IR spectroscopy and H-1 NMR spectroscopy.