In this work, we proposed a facile method for preparation of hierarchical porous ceramic membrane with energetic catalytic ozonation capability aiming at enhancing the performance of water treatment by using the combined ozone-membrane system. The strategy involved preparation of TiO2 macroporous membrane as a backbone and subsequently coating it with mesoporous TiMn catalyst layer. Scanning electron microscope, transmission electron microscope and nitrogen sorption isotherms characterization demonstrated that the TiO2 membrane was composed of TiO2 nanorods with 200400 nm diameter, 5 mu m length, and mesoporous TiMn layer was coated on the membrane surface uniformly with the thickness of about 100 nm and pore size of 10 nm. Energy dispersive X-ray spectroscopy, X-rays photoelectron spectroscopy and X-ray diffractometer showed that TiMn mixed oxide was spread into the inner voids of the membrane to form a hierarchical porous structure. Treating simulated wastewater (aqueous solution of dye Red-3BS and Aniline) it was found that hierarchical porous catalytic membrane exhibited high catalytic ozonation capability which resulted in an enhancement of membrane antifouling, separation and degradation of organic pollutants when the membrane was used as a key device in the combined membrane and ozone system.