It is accepted that the reduction of iodine species in non-aqueous solvents occurs through one-electron or two-electron processes below roughly 3.5 V vs. Li/Li+. In some iodine solutions, the molecular complexation of iodine with the organic solvent proceeded via a charge transfer interaction. Reduction of iodine in non-aqueous solvents having S=O or P=O groups, as well as interactions of iodine molecules with these solvents, were studied. Iodine molecules associated with dimethyl sulfoxide (DMSO), tetramethylene sulfoxide (TMSO), and trimethyl phosphate (IMP) showed anomalous reduction above+1.0 V vs. NHE. We demonstrated the operation of lithium-iodine batteries using DMSO, TMSO and TMP near 4.0 V vs. Li/Li+ (C) 2012 Elsevier B.V. All rights reserved.