Poly(vinyl alcohol) (PVA) is a water-soluble polymer that has been studied intensively because of several interesting physical properties that are useful in technical applications, including biochemical and medical applications. In this article, we report the effects of the addition of gelatin on the optical, microstructural, thermal, and electrical properties of PVA. Pure and PVA/gelatin blend films were prepared with the solution-casting method. These films were further investigated with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, and dielectric measurements. The FTIR spectrum shows a strong chemical interaction between PVA and gelatin molecules with the formation of new peaks. These peaks are due to the presence of gelatin in the blend films. The DSC results indicate that the addition of gelatin to PVA changes the thermal behavior, such as the melting temperature of PVA, and this shows that the blends are compatible with each other. This also shows that the interaction of gelatin and PVA molecules changes the crystallite parameters and the degree of crystallinity, and this supports the XRD results. The UV-vis optical study also reflects the formation of the complex and its effect on the microstructure of the blend film. Moreover, the addition of gelatin also gives rise to changes in the electrical properties of PVA/gelatin blend films. (C) 2008 Wiley Periodicals, Inc.