Polypyrrole-poly(vinyl chloride) composite films are prepared by the modification of the diffusion-oxidative polymerization technique with some treatments. This new technique produces promising flexible and electroactive free standing films. The conductivity profile against the polypyrrole content has a surprising intermediate plateau. This plateau treats the percolation problem and provides an indispensable view on the interfacial phenomenon probably occurs in the binary composite systems. In addition, the temperature dependence of the electrical conductivity is explained in the light of two different hopping mechanisms from which the activation energy and the density of electronic states at the Fermi level are determined, approaching well the values predicted for the semi-conducting materials.