A structural investigation of Agx(Ge0.25Se0.75)100 − x glasses with x = 5, 15, and 25 at.% has been carried out by neutron diffraction and ab initio molecular dynamics (AIMD) simulation. A structural model for the glasses has been proposed: the Ge(Se1/2)4 tetrahedra would remain the fundamental structural units in all samples. The introduction of Ag in the Ge0.25Se0.75 network would lead to a decrease in homopolar SeSe bonds and appearance of GeGe bonds. A strong evolution in the AgAg correlations upon introduction of Ag was observed with the AgAg correlation distances changing from 4.4 Å for the Ag-poor glass to 3.0 Å for the Ag-rich ones. Such information was used to discuss the evolution of conductivity with Ag content in these glasses.