An investigation is carried out on new solid polymer electrolytes based on Polyvinylidene fluoride (PVdF) doped with Ammonium Nitrate (NH4NO3), which have been prepared by solution casting technique using Dimethylformamide (DMF) as solvent. XRD analysis shows the amorphous nature of the polymer electrolytes. AC impedance analysis gives the ionic conductivity value of the electrolytes. The conductivity at room temperature (303K) has been found to be increased by the addition of ammonium nitrate and the maximum value is 1.712x10-5(S/cm) for 80%PVdF: 20% NH4NO3 polymer electrolyte. Dielectric study has been made to analyse the electric behavior of polymer electrolytes. From UV-Vis spectroscopy the direct band gap energy is observed to be 4.16eV & 4.08eV for pure PVdF & salt doped PVdF samples respectively.