Solvation nature of Lithium iodide (LiI) for both polar and nonpolar organic solvents viz., acetonitrile and benzonitrile have been explored by effect of geometry, spectroscopic, conductometric, ab initio methods. Results of vibrational spectroscopic data were compared with experimental values. Centre of attraction is iodide anion on significant vibrational bands of benzonitrile. Fluorescence spectra provide a supporting to the mentioned facts. Ab initio calculations used for shaping the optimum location of Li+ and I- ions in ion solvent interactions containing varying nitriles as solvent sphere. Emission band positions, intensity, shape of solvent-sensitive molecules in organic solvents of varying polarities are studied. (C) 2017 Elsevier B.V. All rights reserved.