Studies on electrochemical preparation of poly(p-phenylene vinylene) (PPV) via electrochemical reduction of alpha,alpha,alpha',alpha'-tetrabromo-p-xylene have been carried out in acetonitrile. Two intermediate species produced en route to the final products have been identified during the spectroelectrochemical experiments. The coulombic efficiencies of the polymerization reaction were shown to be about 45% with no enhancement in deposition rate noticed when the electrode surface was modified by the PPV film. The cations of the supporting electrolyte played a critical role in determining the morphology of the films. The film thus prepared had poor electroactivity as evidenced by the cyclic voltammetric currents for oxidation and reduction of the polymer and low absorbance of the products produced thereof. (C) 2004 Elsevier Ltd. All rights reserved.