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• Electronic polarization and defect engineering modification enhanced intrinsic PMS activation. • ACO-O V @PES membrane/PMS system achieved flow-through removal of contaminants. • The highly accessible SO 4 ·−, · OH, and 1O 2 were the responsible reactive species. • DFT calculations revealed PMS activation promotion by dual-modification strategy. The application of Fenton-like membrane reactors for water purification offers a promising solution to overcome technical challenges associated with catalyst recovery, reaction efficiency, and mass transfer typically encountered in heterogeneous batch reaction modes. This study presents a dual-modification strategy encompassing electron polarization and defect engineering to synthesize Al-doped and oxygen vacancies (O V)-enriched Co 3 O 4 spinel catalysts (ACO-O V). This modification empowered ACO-O V with exceptional performance in activating peroxymonosulfate (PMS) for the removal of organic contaminants. Moreover, the ACO-O V @polyethersulfone (PES) membrane/PMS system achieved organic contaminant removal through filtration (with a reaction kinetic constant of 0.085 ms−1), demonstrating outstanding resistance to environmental interference and high operational stability. Mechanistic investigations revealed that the exceptional catalytic performance of this Fenton-like membrane reactor stemmed from the enrichment of reactants, exposure of reactive sites, and enhanced mass transfer within the confined space, leading to a higher availability of reactive species. Theoretical calculations were conducted to validate the beneficial intrinsic effects of electron polarization, defect engineering, and the confined space within the membrane reactor on PMS activation and organic contaminant removal. Notably, the ACO-O V @PES membrane/PMS system not only mineralized the targeted organic contaminants but also effectively mitigated their potential environmental risks. Overall, this work underscores the significant potential of the dual-modification strategy in designing spinel catalysts and Fenton-like membrane reactors for efficient organic contaminant removal. [Display omitted] [ABSTRACT FROM AUTHOR]