The current work presents an iodine-mediated fine-tuning method for the electrical and electrochemical properties of reduced-graphene oxide (r-GO)/iodine - based electrodes for application in ITO-free polymer solar cells (PSCs). A multi-technique investigation was applied to correlate the morphological features of GO thin films (GO TFs) with iodine adsorption during the reduction process by HI vapor, electrochemical band gap, Fermi potential, charge carrier mobility and charge density of iodine/r-GO based electrodes. The electrical and electrochemical characteristics of iodine/r-GO electrodes changed considerably by alteration of their surface roughness and iodine content. Iodine/r-GO TFs with the lowest surface roughness and the highest iodine content exhibited the highest charge carrier density and Fermi potential. Electrochemical impedance spectroscopy (EIS) and quantum Hall effect (QHE) results confirmed the p-type conductivity of r-GOs/iodine-based electrodes. PSCs were fabricated using r-GO/iodine electrodes as the photo-anode to follow the influences of iodine content and surface roughness on the photovoltaic performance of the cells. PSCs prepared based on r-GO/iodine electrodes possessing the lowest surface roughness and the highest iodine content provided the lowest charge transfer resistance (12(ct)) and remarkably higher (similar to 48%) PCE. (C) 2019 Elsevier Inc. All rights reserved.