Various metal-based heterogeneous catalysts for the activation of peroxymonosulfate have been explored to be highly efficient in the degradation of organic pollutants. However, the secondary contamination hindered their steps for practical application and is the key-problem to be urgently addressed. In this work, catalyst/Al 2 O 3 hollow fibre composites have been developed, which enables the elimination of the secondary contamination by immobilization of catalyst on robust supports instead of powdered catalysts. Ag[sbnd]La 0.8 Ca 0.2 Fe 0.95 O 3-δ /Al 2 O 3 composite hollow fibres were synthesized and showed excellent catalytic effect on methylene blue degradation by advanced oxidation process. TiO 2 /Al 2 O 3 composite hollow fibres were also fabricated to decompose the pollutant via photocatalysis. This study provides a potential strategy enabling ceramic hollow fibre-supported catalysts to remove organic pollutants in aqueous phase effectively, opening a new window of membrane-based catalyst for advanced oxidation in the practical application.