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.