This paper focused on the transport studies of PVA–chitosan blended electrolyte system and application in proton batteries. The electrolytes were prepared by the solution cast technique. In this work, 36wt.% PVA and 24wt.% chitosan blend doped with 40wt.% NH4NO3 exhibited the highest room temperature conductivity. The conductivity value obtained was 2.07×10−5 Scm−1. EC was then added in various quantities to the 60wt.% [60wt.% PVA–40wt.% chitosan]–40wt.% NH4NO3 composition in order to enhance the conductivity of the sample. The highest conductivity obtained was 1.60×10−3 Scm−1 for the sample containing 70wt.% EC. The Rice and Roth model was applied to analyze the conductivity enhancement. The highest conducting sample in the plasticized system was used to fabricate several batteries with configuration Zn//MnO2. The open circuit potential (OCP) of the fabricated batteries was between 1.6 and 1.7V.