Enriching　and　detecting　the　trace　pollutants　in　actual　matrices　are　critical　to　evaluating　the　water　quality.　Herein,　a　novel　nanofibrous　membrane,　named　PAN-SiO2@TpPa,　was　prepared　by　in　situ　growing　β-ketoenamine-linked　covalent　organic　frameworks　(COF-TpPa)　on　the　aminated　polyacrylonitrile　(PAN)　nanofibers,　and　adopted　for　enriching　the　trace　polychlorinated　biphenyls　(PCBs)　in　various　natural　water　body　(river,　lake　and　sea　water)　through　the　solid-phase　micro-extraction　(SPME)　process.　The　resulted　nanofibrous　membrane　owned　abundant　functional　groups　(-NH-,　-OH　and　aromatic　groups),　outstandingly　thermal　and　chemical　stability,　and　excellent　ability　in　extracting　PCBs　congeners.　Based　on　the　SPME　process,　the　PCBs　congeners　could　be　quantitatively　analyzed　by　the　traditional　gas　chromatography　(GC)　method,　with　the　satisfactory　linear　relationship　(R2>0.99),　low　detection　limit　(LODs,　0.1∼5　ng　L−1),　high　enrichment　factors　(EFs,　2714∼3949)　and　multiple　recycling　(>150　runs).　Meanwhile,　when　PAN-SiO2@TpPa　was　adopted　in　the　real　water　samples,　the　low　matrix　effects　on　the　enrichment　of　PCBs　at　both　5　and　50　ng　L−1　over　PAN-SiO2@TpPa　membrane　firmly　revealed　the　feasibility　of　enriching　the　trace　PCBs　in　real　water.　Besides,　the　related　mechanism　of　extracting　PCBs　on　PAN-SiO2@TpPa　mainly　involved　the　synergistic　effect　of　hydrophobic　effect,　π-π　stacking　and　hydrogen　bonding.　©　2023　Elsevier　Ltd