Poly (p-phenylene vinylene) (PPV) was prepared electrochemically from p-xylene-bis (diethylsulphonium chloride) in a solvent-electrolyte couple of acetonitrile-tetrabutylammonium tetrafluoroborate (TBAFB). The polymer obtained from the electrode surface was converted to PPV by the thermal elimination of diethyl sulfide, HCl and ethyl sulfide. PPV was also obtained chemically in order to investigate the effect of the synthetic method on the structure and electrical conductivity. The characterization of the polymers was carried out by means of fourier transform infrared spectrometer (FTIR), differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) techniques. The doping effect on the conductivity of the PPV was investigated by using different agents such as H2SO4, I-2 and metallic Na.