Solid polymer electrolytes based on polyvinyl alcohol (PVA) doped with LiPF6 have been prepared using solution casting technique. Electrical properties of prepared electrolyte films were analyzed using AC impedance spectroscopy. The ionic conductivity was found to increase with increasing salt concentration. The maximum conductivity of 8.94 × 10−3 S·cm−1 was obtained at ambient temperature for the film containing 20 mol% of LiPF6. The conductivity enhancement was correlated to the enhancement of available charge carriers. The formation of a complex between the polymer and salt was confirmed by Fourier transform infrared spectroscopy (FT-IR). The optical nature of the polymer electrolyte films was analyzed through UV-Vis spectroscopy.