Polymeric films based on polyvinyl alcohol (PVA) doped with CoCl, NiCl, and FeCl at different weight percent were prepared using the cast technique. The structural properties of these films were investigated by X-ray diffraction, UV-visible (UV-Vis) double beam scanning spectrophotometer, and vibrating sample magnetometer techniques. PVA shows crystalline nature while highly doped PVA films show amorphous nature, indicating the random distribution of the fillers within the polymeric matrix. It is found that the average of crystalline size and interplanar spacing of PVA vary with different fillers. The UV-visible absorption of the samples shows noticeable change in the band position shifted to higher wave length with the filling level. The PVA/metal chloride composites exhibit a ferromagnetic behavior with low remanent and saturation magnetization at room temperature. [ABSTRACT FROM AUTHOR]