Poly (N-vinyl pyrrolidone) (PVP), Polyvinylchloride (PVC) blend membrane doped with different molar weight percentage of NH4Br has been prepared by solution casting technique using dimethyleformamide (DMF) as solvent and characterized for electrical properties. The prepared polymer electrolyte has been studied by XRD, FT-IR, Dielectric and Capacitance measurements. The XRD results show that the amorphous nature of PVP has increased in 70%PVP: 30%PVC. It is also observed that the amorphous nature of 70%PVP: 30%PVC is further increased by the addition of different concentration of NH4Br. A complex formation of PVP: PVC, PVP: PVC: NH4Br have been confirmed by FT-IR studies. Proton conductivity for the above film has been measured using impedance spectroscopy. The polymer blends 70%PVP: 30%PVC shows an ionic conductivity of 8.46X10-8 Scm-1. The conductivity of the blend film increases as concentration of NH4Br increases. The maximum proton conductivity 2.78X10-3 Scm-1 has been observed for 70%PVP: 30%PVC: 0.6 Molar weights (MWt) NH4Br. The primary proton battery with configuration of Zn + ZnSO4.7H2O/70PVP:30PVC: 0.6 Mwt% NH4Br/PbO2 + V2O5 are fabricated and tested.