A computational method for quantitatively predicting regions of electrochemical stability (potential windows) of organic liquid electrolytes based on ab initio molecular orbital calculations is presented. Potential windows are estimated by calculating the oxidation and reduction potentials of different molecular species present in the electrolyte (namely, individual cations and anions, cation-anion pairs, and individual solvent molecules) and taking the sum of the lowest oxidation and reduction values obtained. Intermolecular interactions between the different species and solvent phase are taken into account using the isodensity polarizable continuum model. Using this method the measured electrochemical potential windows of ten candidate organic liquid electrolytes are reproduced with high accuracy. (C) 2014 The Electrochemical Society. All rights reserved.