Detecting　and　analyzing　of　the　trace　organochlorine　pesticides　(OCPs)　in　the　real　water　has　become　a　big　challenge.　In　this　work,　a　novel　functional　electrospun　nanofiber　membrane　(PAN@COFs)　was　synthesized　through　the　in　situ　growth　of　covalent　organic　frameworks　(COFs)　on　a　polyacrylonitrile　electrospun　nanofiber　membranes　under　room　temperature　and　used　in　the　solid-phase　micro-extraction　(SPME)　to　enrich　trace　organochlorine　pesticides　(OCPs)　in　water.　The　resulted　PAN@COFs　composite　consisted　of　numerous　nanofibers　coated　ample　porous　COFs　spheres　(~　500　nm)　and　owned　stable　crystal　structure,　abundant　functional　groups,　good　stability.　In　addition,　the　enrichment　experiments　clearly　revealed　that　PAN@COFs　exhibited　rather　outstanding　performance　on　adsorbing　the　trace　OCPs　(as　low　as　10　ng　L−1)　with　the　enrichment　of　482–2686　times.　Besides,　PAN@COFs　displayed　good　reusability　and　could　be　reused　100　times.　Notably,　in　the　real　water　samples　(sea　water　and　river　water),　the　high　enrichment　factors　and　recovery　rates　strongly　confirmed　the　feasibility　of　PAN@COFs　for　detecting　the　trace　OCPs.　Furthermore,　due　to　the　synergy　of　π-π　stacking　interaction　and　hydrophobic　interaction　between　the　OCPs　molecules　and　PAN@COFs,　the　OCPs　could　be　efficiently　adsorbed　on　PAN@COFs,　even　under　the　extremely　low　driving　force.　©　2021　Elsevier　B.V.