The interest of self-assembled monolayers (SAM) comes from their wide range of very specific technological applications. The SAMs having a terminal charged group are of great importance as model surfaces for electron transfer studies. The electron transfer for highly charged electroactive ions at a SAM modified electrode involves an electrostatic interaction. The present work studies a negatively charged SAM of 2-mercaptobenzimidazole-5-sulfonate (MBIS). The adsorption of the molecule on polycrystalline gold is described by X-ray photoelectron spectroscopy (XPS) and the reductive desorption of MBIS. The behavior of the MBIS monolayer towards the electron transfer of the ferri/ferrocyanide reaction is investigated by cyclic voltammetry and odd random phase multisine electrochemical impedance spectroscopy (ORP-EIS). This technique ensures reliable experiments and enables a statistically founded modeling. The combined electrochemical and surface study allows the investigation of the characteristics and electrochemical properties of the MBIS monolayer formed on polycrystalline gold to provide a quantitative modeling, which is physically and statistically validated. The major contribution of this work is the use of ORP-EIS and XPS to understand how the interaction between a charged SAM and electroactive ions affects the electron transfer. (C) 2014 Elsevier Ltd. All rights reserved.