AgI‐based Ge–Sb–S, Ga–Sb–S, and Ge–Ga–Sb–S chalcogenide glasses were designed and prepared by melt‐quenching, thereafter their thermal properties and conductive performance were comparatively investigated on the basis of their composition‐induced network structures. Glass transition in each sample was examined by DSC measurements. Results showed that the samples containing Ge had a higher thermal stability than the Ga–Sb–S–AgI sample, and the Ge–Sb–S–AgI sample obtained had the highest conductivity ion. Raman spectrum analysis was performed, and the results indicated that the [GeS4‐xIx] structural units and [SbS3−xIx] pyramids in the matrix produced effective ion transport channel for dissolved conductive Ag+ ions. In the matrix containing Ga, the [Ga(Ge)S4‐xIx] structure was consumed by part of [S3Ga–GaS3] ethane‐like units, which had no contribution to the ion transition framework. The study provided the directions for composition and structure configuration control in effective conductive chalcogenide glasses.