Abstract: Fe³⁺ and Eu³⁺ co-doped TiO₂ (Fe³⁺-Eu³⁺/TiO₂) hollow microspheres were prepared by the sol-gel method and characterized by techniques such as XRD, TEM, BET and XPS etc. Photocatalytic degradation of methylene blue (MB) was used as a probe reaction to evaluate their photocatalytic activity. The results show that the surface of SiO₂ microspheres evenly coated with a layer of TiO₂ and the treatment ultrasound is beneficial to improve the dispersion of the SiO₂@TiO₂ composite microspheres. Part of the Fe³⁺-Eu³⁺/TiO₂ hollow microspheres were collapse, which were obtained through grinding before alcining the SiO₂@TiO₂ composite microspheres. While the better structural integrity of Fe³⁺-Eu³⁺/TiO₂ hollow microspheres were prepared by grinding after calcining or without grinding. XRD and BET analysis indicate that Fe³⁺-Eu³⁺/TiO₂ hollow microspheres exist in the form of anatase and have good mesoporous structure. The co-doping of Fe³⁺ and Eu³⁺ shows a synergistic effect in TiO₂ hollow microspheres, which can decrease the particle size of Fe³⁺-Eu³⁺/TiO₂ hollow microspheres and and increase the specific surface area. When the doping content of Fe³⁺ and Eu³⁺ is 1.0% and 0.5% respectively, Fe³⁺-Eu³⁺/TiO₂ hollow microspheres exhibit the best photocatalytic activity.