This work focuses on the study of Ge rich phases in the Ge–Se chalcogenide glass system. Radiation induced effects particularly related to Ag diffusion in the glasses under the influence of different doses of γ radiation are investigated and documented. Raman spectroscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electron microscopy, and atom force microscopy confirmed the occurrence of radiation-induced Ag diffusion and oxidation of the hosting chalcogenide thin films. This causes Ag surface deposition and structural reorganization of the hosting backbone, and affects the electrical performance of the films. It is suggested that the sensing ability of the thin films can be substantially influenced by the encapsulating the sensing elements to avoid the oxidation of the chalcogenide film.