Results of investigations into the synthesis of heterostructures based on Ge–Si–Sn materials by the method of low-temperature molecular beam epitaxy are presented. The formation of epitaxial films during structure growth has been controlled by the reflection high-energy electron diffraction method. Films with Ge/GeSn, Ge/GeSiSn, and GeSn/GeSiSn heterojunctions are grown with Sn content changing from 2 to 10 % at temperatures in the interval 150–350°С. The stressed state, the composition, and the lattice parameter are studied by the x-ray diffraction method using Omega-scan curves and reciprocal space maps. A tensile strain in the Ge film during Ge/Ge0.9Sn0.1/Si structure growth has reached 0.86%.