Polymer nanocomposites (PNCs) films based on Polyvinylidene fluoride co-hexafluoropropylene (PVDF-HFP), Polyvinylpyrrolidone (PVP), and Ag/ZnO nanoparticles have been prepared using solution casting technique. Investigation of prepared films has been created using various experimental techniques. These prepared films were characterized by XRD, FTIR, UV–visible, and DSC/TGA analysis to study their structural, optical, and thermal properties. The Enhanced amorphous nature of PVDF-HFP/PVP blend film due to doping has been identified from X-ray diffraction analysis. The FTIR spectra confirmed the complexation between the Ag and ZnO ions and the host polymer in terms of changes in intensity and certain band positions. The UV–visible analysis showed that the optical band gap (direct and indirect band gap) of the pristine polymeric blend change significantly with the concentration of dopant Ag/ZnO NPs, and these effects are more noticeable at the higher loading. Variation in glass transition temperature (Tg) and melting temperature (Tm) of PVDF-HFP/PVP-Ag/ZnO PNCs system having various concentration of Ag/ZnO NPs were observed by DSC analysis. The Tg of the composite has been found to be decreasing with increase in the content of Ag/ZnO NPs revealing the ordered arrangement of nanoparticles in the blend. The excellent thermal stability of the blend nanocomposite compared to pure PVDF-HFP/PVP blend and its improvement with the loading of Ag/ZnO NPs has been proved by TGA. From all the characterization results, Ag/ZnO-doped PVDF-HFP/PVP polymer blend exhibits better properties which are more suitable for electrochemical devices.