Highly crystalline MgSn(OH) 6 cubic and polyhedral nanoparticles were synthesized via hydrothermal method by adjusting the ethanol/water ratio. Mg 2 SnO 4 / SnO 2 nanoparticles have been successfully obtained by subsequent calcining, which maintain the original morphologies of the precursor with shrank size and rough surface. The structural properties of Mg 2 SnO 4 /SnO 2 heterostructures were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, UV-Vis absorption spectroscopy, and N 2 adsorption/desorption isotherms. The photocatalytic activity of the Mg 2 SnO 4 / SnO 2 nanoparticles was further evaluated by the degradation of methylene blue (MB) under UV illumination. The obtained results revealed that Mg 2 SnO 4 /SnO 2 polyhedral nanoparticles have excellent performance on photocatalytic degradation of MB. It is assumed that the red shift of band gap, oxygen vacancies, and higher specific surface areas of polyhedral Mg 2 SnO 4 /SnO 2 nanocomposites contribute to the enhancement in the photocatalytic activity.