The occurrence of ultrafiltration (UF) membrane fouling frequently hampers the sustainable advancement of UF technology. Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling. Nevertheless, the self-cleaning process may accelerate membrane aging. Addressing these concerns, we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes. To begin, TiO2 nanoparticles were incorporated into the polymer molecular structure via molecular design, resulting in the synthesis of TiO2/carboxyl-polyether sulfone (PES) hybrid materials. Subsequently, the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane. Lastly, a polyvinyl alcohol (PVA) hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO2/carboxyl-PES self-healing reactive UF membranes. By establishing a covalent bond, the TiO2 nanoparticles were effectively and uniformly dispersed within the UF membrane, leading to exceptional self-cleaning properties. Furthermore, the water-absorbing and swelling properties of PVA hydrogel, along with its capacity to form hydrogen bonds with water molecules, resulted in UF membranes with improved hydrophilicity and active self-healing abilities. The results demonstrated that the water contact angle of PVA@5%TiO2/carboxyl-PES UF membrane was 43.1°. Following a 1-h exposure to simulated solar exposure, the water flux recovery ratio increased from 48.16% to 81.03%. Moreover, even after undergoing five cycles of 12-h simulated sunlight exposure, the UF membranes exhibited a consistent retention rate of over 97%, thus fully demonstrating their exceptional self-cleaning, antifouling, and self-healing capabilities. We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.