In recent years, the development and application of semiconductor materials with excellent photocatalytic properties have been paid wide attention in addressing the issue of water pollution. Hollow nanospheres of titanium dioxide (TiO 2 ), doped with Fe ions, have been fabricated through the hard template method for photocatalytic degradation of organic pollutants. The hierarchical nanospheres were synthesized using hydrothermal carbon spheres as a template, resulting in an average diameter of about 200 nm, a mesoporous structure characterized by a remarkably large specific surface area, and uniform dispersion of Fe on the surface of hollow TiO 2 . In this study, the effect of operating parameters such as catalyst concentration and environmental conditions on the degradation of rhodamine dyes by catalysts was investigated. The optimal Fe dopant content of TiO 2 was 2.0%, exhibiting the highest photocatalytic activity and recyclability under ultraviolet (UV) light irradiation. It can be attributed to the double effects of the oxygen vacancy (OV) defect produced by doped ion modification and more active site of the hollow structure. The results show that Fe−TiO 2 composites can be used as effective photocatalysts to mineralize toxic dye molecules from wastewater.