The thermodynamic properties of Ag8GeTe6 compound and Ag8GeТe6-xSex solid solutions were studied by EMF measurements of the concentration cells concerning to a silver electrode with Ag4RbI5 solid electrolyte in the 300–400 K temperature range. The partial thermodynamic functions of silver in alloys are calculated from the EMF measurements data. Based on the data on solid-phase equilibria in the Ag-Ge-Se-Te system, the potential-forming reactions responsible for these partial molar functions were determined and the standard thermodynamic functions of formation and standard entropies of the Ag8GeТe6 compound and solid solutions of the compositions Ag8GeTe5Se, Ag8GeTe4Se2, Ag8GeTe3Se3, Ag8GeTe2Se4 and Ag8GeTeSe5 were calculated.