In this study we are presenting the results of the surface ionization of LinFn-1 (n=4- 6) clusters on rhenium surface impregnated with fullerenes using the magnetic mass spectrometer. The Li5F4 nanocubic cluster was detected for the first time. We determined values of ionization energies for Li4F3 and Li6F5, they are 4,3±0,2 eV, 4,0±0,2eV, respectively. The ionization energies agreed with theoretical ionization energies obtained by ab initio method, which indicates the excess electron localized in a specific site for non-stoichiometric clusters. The first ionization energy value for the Li4F3 was in accordance with earlier results obtained experimentally using photoionization time-of-flight mass spectrometer. There are currently no reliable experimental data for the ionization energy of Li6F5 cluster.Physical chemistry 2006 : 8th international conference on fundamental and applied aspects of physical chemistry; Belgrade (Serbia); 26-29 September 200