Nanostructured PVA polymer composites are of rapidly growing interest because of their sized-coupled properties. The present article deals with both ZnO and WO3 embedded in a polyvinyl alcohol (PVA) matrix using a solvent casting method. These films were characterized using FTIR, XRD, and SEM techniques. The FTIR spectra of the doped PVA shows shift in the bands, which can be understood on the basis of intra/inter molecular hydrogen bonding with the adjacent OH group of PVA. The phase homogeneity and morphology of the polymer composites have been analyzed using scanning electron microscope (SEM). The crystal structure and crystallinity of polymer nanocomposites were studied by X-ray diffraction technique (XRD). Thus due to the interaction of dopant and complex formation, the structural repositioning takes place and crystallinity of the nanocomposites decreases.