To improve solid-state lithium batteries, solution casting has been employed to create lithium ion-conducting copolymer electrolytes involving poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/polyvinylpyrrolidone (PVP) blend polymers with various compositions. Following X-ray diffraction and Fourier transformation (FTIR), the structural characterisation and identification of molecular bonding in polymer electrolytes were confirmed. Through AC impedance analysis, the electrical characteristics of the solid-state polymer films were investigated. The dielectric conductivity of the sample was found to obey the modified Arrhenius relationship, while in the case of a sample with higher conductivity, it followed Arrhenius behaviour. The relaxation parameters and dielectric behaviour of the samples are demonstrated and discussed.