Developing　adsorbents　with　high　performance　and　long　service　life　for　effective　extracting　the　trace　organochlorine　pesticides　(OCPs)　from　real　water　is　attracting　numerous　attentions.　Herein,　a　self-standing　covalent　organic　framework　(COF-TpPa)　membrane　with　fiber　morphology　was　successfully　synthesized　by　using　electrospun　nanofiber　membranes　as　template　and　employed　as　solid-phase　microextraction　(SPME)　coating　for　ultra-high　sensitivity　extraction　and　analysis　of　trace　OCPs　in　water.　The　as-synthesized　COF-TpPa　membrane　exhibited　a　high　specific　surface　area　(800.83　m2　g−1),　stable　nanofibrous　structure,　and　excellent　chemical　and　thermal　stability.　Based　on　the　COF-TpPa　membrane,　a　new　SPME　analytical　method　in　conjunction　with　gas　chromatography-mass　spectrometry　(GC–MS)　was　established.　This　proposed　method　possessed　favorable　linearity　in　concentration　of　0.05–2000　ng　L−1,　high　sensitivity　with　enrichment　factors　ranging　from　2175　to　5846,　low　limits　of　detection　(0.001–0.150　ng　L−1),　satisfactory　precision　(RSD　＜　10　%),　and　excellent　repeatability　(＞150　cycles),　which　was　better　than　most　of　the　reported　works.　Additionally,　the　density　functional　theory　(DFT)　calculations　and　XPS　results　demonstrated　that　the　outstanding　enrichment　performance　of　the　COF-TpPa　membrane　was　owing　to　synergistic　effect　of　π–π　stacking　effects,　high　specific　surface　area　and　hydrogen　bonding.　This　work　will　expect　to　extend　the　applications　of　COF　membrane　to　captures　trace　organic　pollutants　in　complex　environmental　water,　as　well　as　offer　a　multiscale　interpretation　for　the　design　of　effective　adsorbents.　©　2024