Poly(vinyl chloride) (PVC) has been converted to an electrically conductive structure by combined electrochemical and photochemical methods. PVC was cast on a polypyrrole (PPy) film electrode which had been electrochemically prepared. The PVC layer in the laminated PVC/PPy films was first dehydrochlorinated under the illumination of UV light, and the generated polyenes were subsequently doped with I-2 and FeCl3. The maximum electrical conductivity achieved for such PVC film was 2.51 X 10(-2) and 8.63 10(-2) S cm(-1) after I-2 and FeCl3 doping, respectively. The temperature dependence of the electrical con ductivity showed different behavior in higher and lower temperature ranges. In the former (T > 243 K), the T-1 law held, and the activation energy and bandgap were estimated as 0.25 and 0.49 eV, respectively. In the latter (T < 243 K), the conductivity mechanism followed the variable range hopping model (T--1/4 law) in which the radius of the localized state wave function and the density of the localized states at the Fermi level were 1.25 X 10(3) Angstrom and 1.03 X 10(15) eV(-1) cm(-3), respectively.