Here, hierarchical ZnO nanoflake spheres were hydrothermally synthesized at a large scale. These hierarchical ZnO nanoflake spheres were well characterized and successfully assembled on a piece of polymer membrane surface to form a multifunctional membrane with a win-win aim to realize the mitigation of membrane fouling and reuse of catalysts. This newly developed membrane demonstrated the removal ability of high pollutants via filtration, photodegradation of pollutants, and antibacterial growth under visible light irradiation. At the same time, this novel membrane holds the potential to produce clean water at a constant high flux.