Thermal and structural stability in the glass transition region of chalcogenide glasses has been investigated in terms of thermodynamics for application to various optoelectronic devices. In this study, the compositions of Ge_xSb₂₀Se_80-x (x = 10, 15, 20, 25, and 30) were selected to investigate the glass stability according to germanium ratios. The chalcogenide bulks were fabricated by using a traditional melt-quenching method. Thin films were deposited by a thermal evaporation system, maintaining the deposition ratio of 3~5 A in order to have uniformity. The thermal and structural properties were measured by a differential scanning calorimeter (DSC) and X-ray diffraction (XRD). The DSC analysis provided thermal parameters and theoretical glass region stabilities. The XRD analysis supported the theoretical stabilities because of where the crystallization peak data occurred.