In this work, data on a temperature-dependent thermic and electrical properties in a novel blend polymer electrolyte membranes based on poly(vinyl alcohol) (PVA) and chitosan (CS) doped with H3PO4 at different concentrations were prepared by solution casting method. Their phase behavior and ionic conductivity were studied by DSC, TGA and IS. These membranes exhibit good proton conductivity of the order of 10−2 Scm−1 at 200 °C and the understanding of the H3PO4 at different concentrations effect in the polymer electrolyte membranes is crucial for possible applications in fuel cells. The data have not been reported nor discussed in the research paper to be submitting.