PVA films with various filling levels of CrF3 and MnCl2 were prepared. ESR and UV/VIS optical analysis were used to shed more light on the structural modification that occur due to filling with different levels and/or UV irradiation. The ESR analysis revealed that the spin configuration of CrF3, MnCl2, and CoBr2-filled PVA are different. The filling level dependence of ESR parameters was discussed. The UV-VIS spectral analysis for pure PVA shows absorption bands at 265 and 280 nm, which were assigned to the presence of carbonyl groups. The addition of CrF3 led to the appearance of another bands at 418 and 596 nm. The filling level and/or UV irradiation have no effect on the position of absorption bands but the intensity of these bands has been changed. The addition of MnCl2 led to a new band at about 350 nm due to charge transfer transition. The ligand field parameters and optical energy gaps can be calculated and discussed. The results of optical and ESR analysis indicated that the Cr3+ or Mn2+ are present in its octahedral symmetrical form within the PVA Matrix. SEM micrographs of CrF3 filled PVA is discussed. (C) 2003 Wiley Periodicals, Inc.