Peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs), as a promising technology for water decontamination, are constrained by low reaction kinetics due to limited reaction selectivity and mass transfer. Herein, we designed a nanoconfined FeCo 2 O 4 -embedded ceramic membrane (FeCo 2 O 4 −CM) under flow-through pattern for PMS activation. Confining PMS and FeCo 2 O 4 within nanochannels (3.0−4.7 nm) enhanced adsorption interactions (−7.84 eV vs −2.20 eV), thus boosting mass transfer. Nanoconfinement effect regulated electron transfer pathways from PMS to FeCo 2 O 4 −CM by modulating the active site transformation to �Co(III) in nanoconfined FeCo 2 O 4 −CM, enabling selectively generating 1 O 2 . The primary role of 1 O 2 in the nanoconfined system was confirmed by kinetic solvent isotope experiments and indicative anthracene endoperoxide (DPAO 2 ). The system enabled 100% removal of atrazine (ATZ) within a hydraulic retention time of 2.124 ms, demonstrating a rate constant over 5 orders of magnitude higher than the nonconfined system (3.50 × 10 3 s −1 vs 0.42 min −1 ). It also exhibited strong resilience to pH variations (3.3−9.0) and coexisting substances, demonstrating excellent stability indicated by consistent 100% ATZ removal for 14 days. This study sheds light on regulating electron transfer pathways to selectively generate 1 O 2 through the nanoconfinement effect, boosting the practical application of PMS-based AOPs in environmental remediation and potentially applying them to various other AOPs.