Thin films of CdxPb1 – xS (0 ≤ x ≤ 0.094) substitutional solid solutions of cubic structure B1 (space group Fm
) were prepared by chemical deposition and characterized by X-ray diffraction, scanning electron microscopy, EDX elemental analysis, and Raman spectroscopy. Once the cadmium sulfate concentration in the batch reached some critical value (0.1 mol/L), the films formed involved two autonomous phases: CdxPb1 – xS substitutional solid solutions and hexagonal cadmium sulfide CdyS of structure В4 (space group P63mc). The method and its parameters as proposed are efficient for manufacturing heterostructures in the CdS–PbS system in one-pot deposition.