The preparation of proton conducting-polymer electrolytes based on poly(vinyl alcohol) (PVA)/ammonium acetate (CH3COONH4)/1-butyl-3-methylimidazolium chloride (BmImCl) was done by solution casting technique. The ionic conductivity increased with ionic liquid mass loadings. The highest ionic conductivity of (5.74 +/- 0.01) mS cm(-1) was achieved upon addition of 50 wt% of BmImCl. The thermal characteristic of proton conducting-polymer electrolytes is enhanced with doping of ionic liquid by showing higher initial decomposition temperature. The most conducting polymer electrolyte is stable up to 250 degrees C. Attenuated total reflectance-Fourier Transform Infrared (ATR-FTIR) confirmed the complexation between PVA, CH3COONH4 and BmImCl. Polymer electrolyte membrane fuel cell (PEMFC) was fabricated. This electrochemical cell achieved the maximum power density of 18 mW cm(-2) at room temperature. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.