Gel polymer electrolytes (GPEs) are synthesized by incorporating different wt% (0%, 2%, 4%, 5%, 6% and 8%) of acetamide in poly (ethylene oxide) (PEO) with LiI/I-2. The conformational, electrochemical, photoelectrochemical characteristics of the prepared GPEs are studied. Among the electrolytes, PEO with 5 wt% acetamide shows the highest efficiency (eta = 9.01%) compared to original GPE without acetamide (5.7%) under 85 mW cm(-2) illumination. The increase in open circuit voltage (V-oc) is noticed for gel polymer electrolytes may be due to the reduction in the recombination reaction and increase in the electron life time upon incorporation of acetamide on the PEO. The observed increment in short circuit current density (J(sc)) is attributed to the increase in the ionic conductivity and tri-iodide diffusion coefficient, since incorporation of acetamide on the PEO increases the amorphous nature of the electrolyte. (C) 2015 Elsevier B.V. All rights reserved.