Polyvinyl alcohol (PVA) films filled with various mass fractions of FeCl3 were prepared using a casting method. The structural, electrical and magnetic properties were clarified. The filling level (FL) dependence of certain IR absorption peaks was correlated with the obtained physical parameter characterizing the other properties. The XRD scans revealed a semicrystalline feature of the virgin polymer and an existence of two halos. The FL dependence of the intensity of the two halos was studied. The dc electrical resistivity was measured in the temperature range of 300-400 K. An intrachain one-dimensional interpolaron hopping mechanism was assumed to interpret the electrical conduction. The temperature dependence of the dc magnetic susceptibility exhibited a Curie-Weiss behavior in the range of 90-270 K. The ESR studies of PVA filled with various mass fractions of FeCl3 revealed very complicated spectra due to hyperfine and fine structure. The evolution of the ESR spectra with the FL suggested the distribution of Fe3+ ions in isolated and then aggregated modes within the PVA matrix. (C) 2004 Elsevier B.V. All rights reserved.