In this study, we developed a chalcogenide glassy system comprising (Ag 2 S) x -(0.4Ge-0.3Te-0.3Se) 1-x , where x = 0.05, 0.10, and 0.20. The formation of Ag 2 S and GeSe 2 nanocrystallites with small sizes and the development of GeTe, Ag 2 GeS 3 , TeS, and Se 5.95 Te 1.05 phases with high Ag 2 S contents were confirmed by X-ray diffraction. The Fourier transform-infrared spectra demonstrated the characteristic vibration of Ag–S at 500–600 cm −1 . Kinetic analysis of conductivity suggested that the Meyer–Neldel energy was due to polarons hopping from trap to trap induced by multiple phonon excitation. Tunneling of polarons through the grain boundary when x = 0.1 could be interpreted based on the modified non-overlapping small polaron tunneling model. By contrast, the correlated barrier hopping model was more appropriate for explaining the dominant conduction mechanism when x = 0.05 and 0.2. The lower relaxation times when x = 0.05 and 0.2 indicated a higher rate of polaron hopping. The temperature independence of the relaxation process was confirmed based on the scaling process.