In this study, a novel catalytic ceramic membrane (CCM) applied to couple peroxymonosulfate (PMS) to degrade organic pollutants in wastewater were synthesized by sol–gel method. The CCM was surface-loaded by CoTiO3/TiO2 heterojunction nanoparticles as catalytic layer, achieving an instantaneous oxidation efficiency of 90 % for bisphenol A (BPA, 10 mg/L). The electron shuttle process in the CoTiO3/TiO2 heterojunction was confirmed by theoretical calculations, and strong adsorption (Eads = -5.28 eV) was observed between catalysts and PMS. Differential charge density further suggested the trend of electron transfer from the catalytic layer to the vicinity of PMS, causing an elongation of the peroxy bond of PMS from 1.482 Å to 1.794 Å, which led to the generation of SO4•− and ·OH. Typical non-radical featured by 1O2 was also found in the membrane-base catalytic oxidation system. Finally, the degradation pathways of BPA were elucidated, and the toxicities of degradation products were found to be decreased significantly. The CoTiO3/TiO2 heterojunction modified CCMs couple with PMS could form an efficient synergistic coupling system, which has excellent oxidation to various organic pollutants. This research on the properties and mechanism of the CCMs could provide technical and theoretical backing for efficient oxidation treatment of dissolved organic pollutants in wastewater.