Polymer blending is one of the most important methods used to obtain new polymeric materials, and it is a useful technique for designing electrolyte materials with required modifications in the properties, such as electrical, thermal and mechanical. PVP-PVC blend membrane doped with different molar weight percentage of NH4SCN has been prepared by solution casting technique using DMF as solvent. XRD, FTIR, DSC and AC impedance studies have been made for the above membrane. XRD studies reveal the amorphous nature of membrane. A complex formation has been confirmed by FTIR studies. Differential scanning calorimetry shows that the thermal stability and the glass transition temperature decreases with the increase in concentration of ammonium thiocyanate. The maximum proton conductivity of the polymer electrolyte is determined by AC impedance spectroscopy. A maximum conductivity of 4.01 x 10(-4) S cm(-1) has been observed for the composition of 70PVP:30PVC:0.3 M wt% of NH4SCN. Dielectric and modulus behaviors have been studied for the above membrane and the relaxation frequency (tau) is calculated from the loss tangent spectra (tan delta). The primary proton battery with configuration Zn + ZnSO4 center dot 7H(2)O/70PVP:30PVC:0.3 M wt% NH4SCN/PbO2 + V2O5 are fabricated.