This study presents the development of a novel hierarchical porous catalytic membrane for the efficient removal of emerging organic microcontaminants from water. The membrane, inspired by the functional attributes of lymphatic vessels, is based on a nitrogen-rich conjugated microporous polymer (PTPA) synthesized using electrospinning and in situ polymerization. The membrane features a thin layer of crosslinked PTPA nanoparticles (≈1.7 μm) covering interconnected electrospun nanofibers, creating a hierarchical channel system. This system effectively activates peroxymonosulfate (PMS) to generate 98.7% singlet oxygen (¹O₂), enabling durable and highly efficient degradation of microcontaminants. The presence of mesoporous structures between PTPA nanoparticles and macroporous channels enhances mass transfer efficiency and supports high flux rates. The prepared hierarchical porous organic catalytic membrane demonstrates superior performance with a permeance >95% and >2500 L m⁻² h⁻¹ bar⁻¹, sustained over 100 hours. This work introduces an innovative pathway for the design of high-performance catalytic membranes for the removal of emerging organic microcontaminants.This study presents the development of a novel hierarchical porous catalytic membrane for the efficient removal of emerging organic microcontaminants from water. The membrane, inspired by the functional attributes of lymphatic vessels, is based on a nitrogen-rich conjugated microporous polymer (PTPA) synthesized using electrospinning and in situ polymerization. The membrane features a thin layer of crosslinked PTPA nanoparticles (≈1.7 μm) covering interconnected electrospun nanofibers, creating a hierarchical channel system. This system effectively activates peroxymonosulfate (PMS) to generate 98.7% singlet oxygen (¹O₂), enabling durable and highly efficient degradation of microcontaminants. The presence of mesoporous structures between PTPA nanoparticles and macroporous channels enhances mass transfer efficiency and supports high flux rates. The prepared hierarchical porous organic catalytic membrane demonstrates superior performance with a permeance >95% and >2500 L m⁻² h⁻¹ bar⁻¹, sustained over 100 hours. This work introduces an innovative pathway for the design of high-performance catalytic membranes for the removal of emerging organic microcontaminants.