It has already been shown that LDI TOFMS is a powerful and useful technique to generate and study clusters of various solid materials including chalcogenide glasses, which are known due to their high (non)linear refractive indices, broad transmission window in IR spectral region, and photosensitivity to light exposure. This advance material has broad applications in the fields such as infrared optics, electronics, micro-electronics, telecommunication systems and medicine. Mass spectra generated from (GeSe2)100-x(Sb2Se3)x glasses’ powder samples are quite complex with several clusters overlap. Stoichiometry of clusters detected in plasma was determined via comparison of experimental isotopic envelopes with theoretical models. In positive ion mode, Sb+, Se2+, Sb3+, GeSec+, (c = 1-2), SbSec+ (c = 1-2), Sb2Sec+ (c = 1-4), GeaSb3+, Sb3Sec+ (a = 1-4, c = 1-4), Sb3Se5+, GeSbbSe+ (b = 4-5), GeSbSe2+, and Ge9Sb2Sec+ (c = 5-7) entities were detected. In negative ion mode, Sec- (c = 2-3), SbSec- (c = 1-3), Sb2Sec- (c = 3-4), and GeSbSec- (c = 3-5) entities were identified. Some of clusters such as GeSec+ (c = 1-2), SbSe3-, Sb2Sec+ (c = 1-4), and Sb2Sec- (c = 3-4) identified by LDI TOFMS, could be considered to be structural fragments of the glasses’ original structure. This was also proved by Raman spectroscopy.