A setup is developed for measuring the thermal properties of Ag2Te and Ag2Se near the main phase transition and in the region of it in high vacuum. The samples are of stoichiometric composition with an excess of Ag, Te, and Se. Differential thermal analysis is performed and the temperature differences across and along the samples are measured by the pulsed light method. Using data on the thermal diffusivity a(T), the temperature dependence of the thermal conductivity K = apc is determined, where p is the density and c is the specific heat. The measurement technique used allows us to establish that the main phase transitions are accompanied by intense heat release. New phase transitions before and after the main structural phase transition with heat absorption are found. According to the DTA data, in the Ag2Te sample with an excess of Ag (0.25 at.%, cn = 1.2 × 1019 cm−3) the phase transition at 365 K is also accompanied by heat absorption. Thus, it is established that all of the phase transitions in Ag2Te and Ag2Se are first-order.