The crystal structure, surface morphology, and optical properties of thin films made from a blend of polyvinylidene fluoride (PVDF) and poly(vinyl alcohol) (PVA), which were doped with zinc oxide nanoparticles (ZnO NPs) at weight ratios of 2, 4, 6, and 10 wt%, were investigated using the solution blending method. Undoped and doped PVDF-PVA polymer blend thin films were deposited using the spin-coating technique. The effect of the addition of ZnO NPs to PVDF-PVA polymer blends was investigated using X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), and UV-Vis spectroscopy to characterize the crystal structure, surface morphology, and optical properties of thin films. XRD results showed that the addition of ZnO NPs made the PVDF-PVA polymer blend less crystalline. FE-SEM images reveal that the size of ZnO NPs ranges from 35 to 125 nm, which aligns with the results obtained from the Scherrer equation. The optical energy band gap of the PVDF-PVA polymer blend decreases as the doping weight ratios of ZnO NPs increase, which is confirmed by the UV-Vis spectroscopy results.