The electrolyte solution structure for acetonitrile (AN)-lithium salt mixtures has been examined for highly dissociated salts. Phase diagrams are reported for (AN)(n)-LiN(SO2CF3)(2) (LiTFSI) and -LiPF6 electrolytes. Single crystal structures and Raman spectroscopy have been utilized to provide information regarding the solvate species present in the solid-state and liquid phases, as well as the average solvation number variation with salt concentration. Molecular dynamics (MD) simulations of the mixtures have been correlated with the experimental data to provide additional insight into the molecular-level interactions. Quantum chemistry (QC) calculations were performed on (AN)(n)-Li-(anion)(m) clusters to validate the ability of the developed many-body polarizable force field (used for the simulations) to accurately describe cluster stability (ionic association). The combination of these techniques provides tremendous insight into the solution structure within these electrolyte mixtures. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.035209jes] All rights reserved.