We report a large-scale self-etching approach for the synthesis of monodispersed mesoporous F-TiO2 hollow microspheres. The self-etching derived from HF was elucidated by the morphology, chemical composition, and crystal size evolutions from solid to hollow microspheres with the increase in the concentration of H2SO4. The resulting TiO2 hollow microspheres exhibited ease for the concurrent membrane filtration and photocatalysis, providing high potential for engineering application in advanced water treatment, for not only increasing water production but also improving water quality.