Covalent organic framework materials (COFs) are promising for pollutant adsorption owing to their high specific surface area, tunable pores and functional designability, but their microcrystalline powder form leads to poor mechanical strength and processability, limiting practical applications. This study presents a mild, eco-friendly strategy using polysulfonamide fiber (PSA) with excellent mechanical and thermal stability as the core matrix, and room-temperature-synthesized sulfonic acid-functionalized TFP-DABA-COFs as the shell layer. Via coaxial wet spinning, core–shell structured PSA-COF composite fibers were fabricated without harsh solvothermal conditions, improving COF dispersion and interfacial bonding. Characterizations revealed the fibers possessed favorable comprehensive properties: fracture strength of 14.97 MPa, elongation at break of 32.84%, specific surface area of 8 m²/g, and hierarchical porous structures dominated by micropores, with enhanced hydrophilicity beneficial to aqueous adsorption. Adsorption experiments on woven fabrics showed 93.6% methylene blue removal in 40 min and 98.9% in 120 min, following the quasi-second-order kinetics, indicating chemisorption (electrostatic attraction) as the main mechanism. This work provides a mild, green approach to prepare PSA-COFs core–shell fibers, effectively solving the formability and processing issues of COFs.

Covalent Organic Frameworks (COFs) are renowned for their high crystallinity and tailored porosity, yet their intractable powder form and poor processability severely limit practical deployment. While electrospun nanofiber membranes offer a pathway to macro-scale COF composites, they often suffer from isotropic mechanical weakness and lack textile processability. Herein, we report a conjugated electrospinning strategy integrated with in situ solvothermal synthesis to fabricate continuous, weavable, and mechanically robust Polyacrylonitrile@Covalent Organic Framework-H (PAN@COF-H) composite yarns. The resulting yarns feature a unique hierarchical architecture where COF-H crystals uniformly coat the surface of oriented nanofibers. This design endows the material with a high specific surface area (94.9 m²/g) and exceptional tensile strength (10 MPa), representing a significant improvement over conventional random electrospun mats. Benefiting from the intrinsic porosity of COF-H and the hydrophilic nature of the composite, the yarns achieve a 73.76% removal rate for Rhodamine B (RhB) within 4 h. Crucially, the material retains over 33.36% of its adsorption capacity after five consecutive cycles, demonstrating outstanding durability. This study bridges the gap between microscopic COF crystals and macroscopic textile architectures, offering a versatile platform for deployable environmental remediation technologies.