Abstract—Sulfide-conducting ionic salts: calcium thioyttrate and thioytterbate and barium thiosamarate with the citrate-nitrate prehistory and also a semiconducting dopant, zirconium disulfide, are synthesized. The conditions are selected for preparation of heterogeneous mixtures CaY2S4–ZrS2 (I), BaSm2S4–ZrS2 (II), and CaYb2S4–ZrS2 (III). Attestation of samples by XRD and SEM methods revealed the formation of new compounds Y2ZrS5 and BaZrS3 in heterogeneous systems (I) and (II), respectively, and the formation of a solid solution based of calcium thioytterbate in system (III) containing up to 10 mol % ZrS2. TGM and DTA studies attest of thermal stability of all these systems in air. The temperature and concentration dependences of the electrical conductivity of heterogeneous mixtures are studied. Substantial increase in conductivity of heterogeneous mixtures (I) and (II) in the composition region from 20 to 40 mol % ZrS2 and the decrease in conductivity upon addition of 2–40 mol % ZrS2 into calcium thioytterbate (system III) are observed.