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Electroinitiated polymerization of the bis(2,6-dibromo-4-chlorophenoxo)-N,N,N',N'-tetramethylethylenediamine copper(II) complex was accomplished upon anodic oxidation in acetonitrile. Anodic and cathodic peak potentials of the complex were measured by cyclic voltammetry (CV) in advance. Constant potential electrolyses carried out at peak potentials yielded polymers only in the anolyte. The presence of polymers in the anode compartment and the effect of radical inhibitor indicated a free-radical mechanism. In the absence of current, the complex in acetonitrile did not yield any trace of polymer for 10 days. The electrochemically produced radicals were very stable. When the polymerization was started by electroinitiation, it continued after discontinuance of the current. In order to follow the rate of monomer consumption, CV was employed. Use of six electrodes, in the specially designed H-type cell, allowed in situ, simultaneous monitoring of the monomer concentration. The structure of the polymer was studied by 1H-NMR, 13C-NMR, and FTIR spectral analyses. Molecular weight measurements were carried out by the isopiestic method.