Structural properties of the AgSbTe 2 -AgSbSe 2 pseudobinary system were examined using thermal analysis, scanning electron microscopy, and x-ray powder diffractometry. It was found that partial substitution of Te by Se atoms leads to stabilization of the cubic crystal structure of alloys. The electronic-transport properties of materials were measured in order to investigate carrier conduction, band-gap features, and thermoelectric properties. The undoped homogeneous solid solution exhibits extremely low thermal conductivity of 0.5 W m −1 K −1 , a very large positive Seebeck coefficient of about 400-600 V K −1 at room temperature, low carrier densities of 10 16 -10 18 cm −3 , and thermally activated conduction. The influence of alloying on thermal-conductivity mechanisms and electron properties was discussed. The highest experimental dimensionless figure of merit ZT of the undoped AgSbSe 0.25 Te 1.75 sample is about 0.65 at a temperature of 520 K. The influence of doping on enhancement of thermoelectric properties of these materials was analyzed and optimal values of transport parameters were estimated.