The vaporization of LiI, LiI/C 70 and LiI/LIF/C 70 was studied using a Knudsen cell located in the ionization chamber of a magnetic sector mass spectrometer in the temperature range from 350 °C to 850 °C. The ion species, Li n I + (n = 2, 3, 4 or 6) were identified from the mixture LiI/C 70 , while the clusters Li n I + and Li n F + (n = 2, 3, 4, 5 or 6) were detected from a mixture LiI/LiF/C 70 . The intensities of Li n I + were higher than the emission of Li n F + cluster when the ratio of LiI to LiF was 2:1. By contrast, the emission of Li n F + is favored when the ratio of LiI to LiF was 1:2. These results show that the vaporization of a mixture LiI/LIF/C 70 from a Knudsen cell located in the ionization chamber of a mass spectrometer represents an efficient and simple way to obtain and investigate clusters of the type Li n X, X = F or I. In this work, it was also shown that the trends of the In (Intensity, arb. units) versus temperature for all Li n I + clusters below and above the melting point of LiI were not same. This suggested that the manner of formation of these clusters could be different due to changes in temperature.