Abstract: Composite materials CaY₂S₄–ZrS₂ and BaSm₂S₄–ZrS₂ synthesized from oxide precursors by ceramic and citrate–nitrate methods, are certified with X-ray diffraction analysis and electron microprobe analysis with subsequent mapping. The use of citrate–nitrate conditioning of the BaSm₂S₄–ZrS₂ composite samples leads to the product contamination, while ceramic conditioning allows obtaining heterogeneous system: solid solution of samarium sulfide in barium thiosamarate and zirconium-containing phases ZrS₂ and BaZrS₃. According to the mapping data, the CaY₂S₄–ZrS₂ system with ceramic sample conditioning, containing more than 5 mol % ZrS₂, contains two phases: CaY₂S₄ and Y₂ZrS₅. The ceramic conditioning of composite materials is shown to increase the electrical conductivity by 2–2.5 orders of magnitude as compared to the basic ionic salts; whereas the sol–gel conditioning, only by 1–1.5 orders of magnitude. The study of the contribution of ionic conductivity made it possible to characterize the BaSm₂S₄–ZrS₂ material containing up to 5 mol % of dopant as ionic conductor; containing 10–30 mol % of dopant, a mixed ionic–electronic conductor. In the CaY₂S₄–ZrS₂ composite material, the ionic contribution prevails in its conductivity. The effect of the dopant on the nature of ionic conductivity is investigated. In the CaY₂S₄–ZrS₂ and BaSm₂S₄–ZrS₂ heterogeneous mixtures, the predominant sulfide-ionic transfer of basic barium thiosamarate and calcium thioitrate is retained; however, the fraction of cationic transfer somewhat increased.