Proton-conducting polymer blend electrolytes based on PVA-PVP-NH4NO3 were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T (g) with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 x 10(-3) S cm(-1) at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH4NO3 with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (epsilon*) and the relaxation frequency (tau) was calculated from the loss tangent spectra (tan delta). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO4 center dot 7H(2)O/50PVA:50PVP:30 wt% NH4NO3/PbO2 + V2O5 was fabricated and their discharge characteristics studied.