The neutrals of the LinI (n = 2-6) clusters were detected using Knudsen-cell which was placed into ionization chamber of the magnetic sector mass spectrometer. The first theoretical and experimental data on the Li3I and Li5I clusters were presented in this Letter. The ionization energies of the neutral of Li3I and Li5I clusters, obtained by the electron impact ionization mass spectrometry, were (5.14 +/- 0.25) and (4.62 +/- 0.25) eV, respectively. We report the geometry, ionization energies and thermodynamical stability of these clusters, calculated at the restricted coupled cluster RHF-RCCSD/cc-pVTZ(Li), cc-pVTZ-PP(I) level of theory. (C) 2012 Elsevier B. V. All rights reserved.