Bis(4-bromo-2,6-dichlorophenoxo) ethylenediamine copper(II) complex has been polymerized using electro-initiation by constant potential electrolysis, in dimethylformamide-tetrabutylammonium fluoroborate solvent-supporting electrolyte couple, at room temperature under air or N2. The process leads to low molecular weight (5.6 x 10(3)) linear poly(dichlorophenylene oxide). The structures of the polymers were determined by H-1-NMR and C-13-NMR. The kinetics of the polymerization were followed by in situ cyclic voltammetry measurements during electrolysis. Unlike thermal polymerization of this complex, the polymerization by electro-initiation begins immediately.