Fluorinated SnO₂ 3D hierarchical structures assembled from nanosheets were synthesized via hydrothermal treatment of stannous fluoride in the presence of an appropriate amount of adipic acid. The as-prepared products were characterized in detail by FESEM/TEM/XRD/BET/XPS/UV-vis DRS techniques. The SnO₂ nanosheets with tetragonal rutile structure were single-crystalline in nature and the exposed planes should be {11} facets. A small amount of fluorine ions was observed to be adsorbed on the surface of SnO₂ physically. It was found that both of F⁻ and adipic acid played important roles in the formation of SnO₂ nanostructures. The as-prepared product presented excellent photocatalytic degradation of RhB which reached 100% within 20 min under UV light irradiation.