The orthorhombic Nb2O5 rectangle nanosheets are synthesized by hydrothermal topological reaction. The orthorhombic Nb2O5 rectangle nanosheet crystals dominantly exposed (010) facet show high UV photocatalytic activity and photoelectric conversion efficiency. The evolution mechanism of crystal structure of orthorhombic Nb2O5 rectangle nanosheets from the layered K4Nb6O17∙4.5H2O precursor is proposed.