The advantages of using the ternary system based on the association of phosphotungstic acid (PWA) and orthophosphoric add (H3PO4) in a polyvinyl alcohol (PVA) organic matrix as an interesting protonic electrolyte have been investigated in the frame of their applicability in all-solid state primary cell manufacturing. The developed electrolyte materials have been studied by X-ray diffraction (XRD), infrared Fourier transform spectrometry (FTIR) and electrochemical impedance spectrometry (EIS). High ionic conductivities ranging from 1.0 to 1.8 10(-2) S cm(-1) could be reached at room temperature for relative humidity ranging from 30 to 100% with a ternary PVA-PWA (40 wt.%)-H3PO4 (40 wt.%) complex. As a consequence of their overall good electrochemical but also mechanical properties, such materials have been used successfully as solid state protonic electrolyte in Zn-MnO2 cell prototype development with arienergy density up to 120 Wh kg(-1). (C) 2014 Elsevier B.V. All rights reserved.