Poly(vinylidene fluoride) (PVDF) films filled with BiCl3 in the mass fraction range of 0.1 <= W <= 10 were prepared. alpha- and beta-Crystalline PVDF phases were detected and characterized by spectroscopic analysis. Fourier transform infrared analysis detected the presence of alpha- and beta-phase head-to-head and tail-to-tall polymer chain defects. The band detected at 1670 cm(-1) was assigned to C=C, indicating polarons in the polymeric matrix. The degree of crystallinity increased by increasing the filling level (FL), and the maximum relative beta-phase content was found at w = 5% FL. This result was confirmed by X-ray diffraction (XRD) and differential scanning calorimetry (DSC) analysis. The Xray analysis confirmed the presence of alpha and beta phases, and no peaks corresponding to pure BiCl3 were found. DSC therograms showed a sharp endothermic peak at T-1 = 444 K for different FLs because of the melting. This peak was used to calculate the activation energy and the order of the reaction. The DC electrical resistivity was attributed to the one-dimensional interpolaron hopping mechanism. The FL dependence of log p and hopping distance (R-o) at 373 K was observed, indicating the FL affected the distribution of the hopping sites. (c) 2006 Wiley Periodicals, Inc.