Abstract Electrochemical cells of the type (Ag | Ag+ electrolyte | Ag-Sb-compounds) have been applied to determine the thermodynamic properties of the intermetallic compounds in Ag-Sb system. Both AgI and β"-alumina were used as fast Ag+ ion conducting solid electrolytes. The usage of these two different electrolytes, in their respective ionic conduction domains, allowed emf measurements in the Ag-Sb system over a significantly wide temperature range. For the first time, emf values of the intermetallic compounds in the Ag-Sb system have been measured above 450 K. Several different cell arrangements were applied to ensure reproducibility of the experiments and to evaluate the effects of different cell arrangements. The parasitic cell potential contributions to the emf values, resulting from thermovoltage and contact potential differences were measured by using symmetric cells. The results obtained with the symmetric cells were analyzed and compensated from the measured emf values of the actual experimental electrochemical cells.