Ab initio molecular dynamics (MD) simulations of the solvation of LiI3 in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I-3(-) ion in relation to X-ray photoelectron spectroscopy (XPS). Simulations show that hydrogen-bond rearrangement in the solvation shell is coupled to intramolecular bond-length asymmetry in the I-3(-) ion. By a combination of charge analysis and I 4d core-level XPS measurements, the mechanism of the solvent-induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent-dependent structure of the I-3(-) ion, and the geometric structure has been correlated with the electronic structure.