A polymer electrolyte of PVA (Polyvinyl alcohol) doped with Tin (II) Bromide (SnBr2) at different weight ratios was synthesized by casting technique. The structure analysis of the composites was displayed by XRD (X-ray diffraction) and F.T. (Fourier transform)-IR techniques, which showed the decrement in the crystallinity with the argument of SnBr2 concentration and functional interaction between SnBr2 and PVA, respectively. The absorbance (Abs.) and transmittance (T%) in the range of wavelength 190− 2500 nm were documented through the UV–vis spectrophotometer to research the influence of SnBr2 on the optical performance of PVA. The incorporation between SnBr2 and the main chain of the PVA matrix brings out a notable change in the optical properties of the polymer electrolytes. The optical band gap, refractive index (n), extinction coefficient (k), the real and imaginary parts of dielectric constant (εr and εi) as well as optical conductivity (σop) exposed a clear dependence on the SnBr2 content. Moreover, the dependence of dielectric properties on the contents of SnBr2 has been studied in the range of frequency from 100 Hz to 1 MHz. The conduction mechanism is mainly correlated Barrier Hopping (CBH) model. SnBr2/(PVA) polymeric solid electrolyte can be used for electronic and optoelectronic and electrochemical devices.