In the presented work, the conditions of the high-temperature and mechanochemical method for the synthesis of compound Sm ₅VO ₁₀ and their influence on its physicochemical properties were studied. The following methods were used for the study: X-ray powder diffraction (XRD), differential thermal analysis (DTA), infrared spectroscopy (FTIR), ultraviolet and visible light spectroscopy (UV–VIS–DRS), scanning electron microscopy (SEM-EDX), and laser beam diffraction spectrometry (LDS). Based on the results, it was determined that the compound Sm ₅VO ₁₀ is thermally stable in air atmospheres up to 1475 °C, crystallises in a monoclinic system, and its structure is made up of oxygen VO ₄ and SmO ₈ polyhedra. The estimated energy gap value for nanometric, mechanochemically obtained Sm ₅VO ₁₀ was about 3.20 eV, and for the microcrystalline, obtained with the high-temperature method, was about 2.75 eV. The established physicochemical characterisation of Sm ₅VO ₁₀ initially showed that the compound could find potential applications, e.g. as a photocatalyst for water purification or as a component of new optoelectronic materials.