A free standing electrolyte film containing poly glycidyl methacrylate (PGMA) as polymer host, lithium perchlorate (LiClO4) as charge carrier and ethylene carbonate (EC) as plasticizer were successfully prepared with solution casting technique. Nuclear magnetic resonance spectroscopy (NMR) was used to investigate the chemical structure of the polymer. The analyses of polymer electrolytes were performed by impedance spectroscopy (EIS), linear sweep voltammetry (LSV) and fourier transform infrared spectroscopy (ATR-FTIR). The solid polymer electrolyte exhibited the highest conductivity at room temperature and 373 K with the values of 3.4 x 10(-4) S cm(-1) and 1.2 x 10(-3) S cm(-1) at 80 wt.% of EC, respectively, in the presence of 80 wt.% of EC. FTIR spectroscopy analysis confirmed the interaction between lithium salt and oxygen atoms in polymer host in the presence of EC. Moreover, the electrolytes containing EC showed good electrochemical stability (-1500 to 3000) mV which reveals the potential of this polymer electrolyte for photoelectrochemical cell (PEC) application. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.