A series of iron doped three-dimensional (3D) ordered macroporous TiO₂ hybrid materials (Fe–Ti–Oxide-M) have been successfully prepared by using polymethylmethacrylate nanospheres (PMMAs) as templates. The crystal structure of Fe–Ti–Oxide-M (50%) could be assigned to the Fe₃Ti₃O₁₀ phase by XRD characterization. Synthetic samples were also studied by TEM and UV-vis absorption spectra in detail. All obtained samples possessed 3D ordered macroporous structures, and the absorption spectra of Fe–Ti–Oxide-M gradually extended to the visible light region with increased doping quantities of Fe. Furthermore, the photo-catalytic degradation of tetracycline (TC) was investigated, and the observed photo-catalytic performances of Fe–Ti–Oxide-M (1%, 2%, 5%, 10%, 20%, and 50%) were associated with their composition, which further indicates that the introduction of Fe has a remarkable influence on the photo-activity of 3D ordered macroporous TiO₂ materials.