The resolution of membrane fouling issues is crucial for the commercial application of membrane distillation (MD) ammonia recovery. The peroxymonosulfate-based advanced oxidation process (PMS-AOP) exhibited conspicuous degradation of organic pollutants, and in-situ coupling with the MD process could probably achieve desirable antifouling performance. In this research, a novel γ-FeOOH@PVDF catalytic membrane was fabricated by gas–liquid self-deposition method and fluorination treatment. The γ-FeOOH nanosheets arrayed on the substrate membrane endowed the catalytic membrane with superhydrophobicity. The MD ammonia recovery of the digestate achieved a high recovery rate (97.3%), and no membrane fouling or wetting phenomena were detected by real-time monitoring by optical coherence tomography (OCT). The batch degradation experiments of thiamphenicol (TAP) validated the γ-FeOOH@PVDF/PMS system with superior degradation performance and stability. The electron paramagnetic resonance (EPR) coordinated free radical quenching experiment determined the active substance (SO4•-, 1O2, O2•- and •OH) in the degradation process. In addition, the potential self-cleaning mechanism of the radical and non-radical pathways of γ-FeOOH@PVDF was elucidated via density functionaltheory (DFT) calculation. The quinone groups in the organic pollutants facilitated the redox of Fe(Ⅲ)/Fe(Ⅱ) and accelerated the activation of PMS. Hence, the catalytic membrane developed in this research provided a novel instructive strategy for membrane fouling control and also exhibited significant potential of coupling catalysis and membrane technology for water treatment.