In order to systematize the knowledge on thermodynamic stability and thermoelectric properties of AgSbTe 2 -based alloys, several experiments examining the influence of thermal treatment on their structural and thermoelectric properties were performed. Samples with a nominal composition of AgSbTe 2 and AgSbTe 1.98 Se 0.02 were prepared and then annealed in various temperature conditions. It was confirmed that Ag 1Àx Sb 1+x Te 2+x (b phase) is the only thermodynamically stable ternary compound in the Ag 2 Te-Sb 2 Te 3 pseudobinary system. It was also proved that thermal stability of b phase is limited-it slowly decomposes below 633 K. In contrast to some reports, it was also indicated that a small amount of Se does not lead to stabilisation of AgSbTe 2 crystal structure. Despite slow kinetics of the decomposition processes, thermoelectric properties of the material are notably affected by thermal treatment and amount of Ag 2 Te precipitations. Maximal ZT value of prepared materials varies from 0.65 at 575 K to 1.07 at 563 K.