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.