Proton conducting polymer electrolytes is based on poly vinyl alcohol doped with glycine and different molar ratios of ammonium thiocyanate that have been prepared by solution casting technique using distilled water as solvent. Increase of amorphous nature of electrolyte system has been confirmed by XRD analysis while increasing the salt concentration. The FTIR analysis confirms the complex formation between the polymer, glycine and ammonium thiocyanate. From the ac impedance studies, it has been found that PVA -1 g and glycine - 0.1 and NH4SCN - 0.7 molar mass percentage (g/mol (m.m.%)) has maximum conductivity of the order of 10(-3) S/cm at room temperature (303 K). The temperature dependent conductivity of the prepared polymer electrolyte obey the Arrhenius relation and the activation energy of the polymer electrolyte lie within 0.62-0.09 eV for all the prepared electrolyte system. Using DC Wagner's polarization method the ionic transference number has been measured for highest conductivity polymer film and the result indicates that the conductivity of the electrolyte is predominantly due to ions. The highest ionic conductivity sample has been used to construct the primary proton battery and the cell parameters have been calculated. (C) 2016 Elsevier B.V. All rights reserved.