Morphological characteristics of poly(vinylidene fluoride) (PVDF) films, filled with mass fractions (w ≤ 20%) of Barium Chloride (BaCl2), were investigated by X-ray diffraction (XRD), Fourier transform infrared (FTIR) absorption spectra and differential scanning calorimetry (DSC) measurements. The dielectric properties of films were measured from 250 Hz to 1 MHz range between 100 and 400 K as a function of frequency and temperature. Spectroscopic data revealed that the filled and unfilled films include a-, b-, and c-crystalline phases. By a 20% filling, 73% increase was obtained in the total degree of crystallinity. Since the BaCl2 formed fluorine bridges over the chain segments on the crystal lamellar surface, the c-crystalline phase decreased, whereas the total degree of crystallinity increased. Dielectric measurements showed that maximum of the dielectric loss factor belonging to b-relaxation transition decreased linearly with filling level. The filling process did not have any effect on the real dielectric constant till a-relaxation transition region. However, in the a-relaxation transition region, it was determined that the real dielectric constant increased linearly with filling level. POLYM. COMPOS., 31:1782–1789, 2010. a 2010 Society of Plastics Engineers