Background:　Accurate　quantitative　analysis　of　small　molecule　metabolites　in　biological　samples　is　of　great　significance.　Hydroxypolycyclic　aromatic　hydrocarbons　(OH-PAHs)　are　metabolic　derivatives　of　emerging　pollutants,　reflecting　exposure　to　polycyclic　aromatic　hydrocarbons　(PAHs).　Macromolecules　such　as　proteins　and　enzymes　in　biological　samples　will　interfere　with　the　accurate　quantification　of　OH-PAHs,　making　direct　analysis　impossible,　requiring　a　series　of　complex　treatments　such　as　enzymatic　hydrolysis.　Therefore,　the　development　of　matrix-compatible　fiber　coatings　that　can　exclude　macromolecules　is　of　great　significance　to　improve　the　ability　of　solid-phase　microextraction　(SPME)　technology　to　selectively　quantify　small　molecules　in　complex　matrices　and　achieve　rapid　and　direct　analysis.　Results:　We　have　developed　an　innovative　coating　with　a　stable　macromolecular　barrier　using　electrospinning　and　flexible　filament　winding　(FW)　technologies.　This　coating,　referred　to　as　the　hollow　fibrous　covalent　organic　framework@polyionic　liquid　(F–COF@polyILs),　demonstrates　outstanding　conductivity　and　stability.　It　accelerates　the　adsorption　equilibrium　time　(25　min)　for　polar　OH-PAHs　through　electrically　enhanced　solid-phase　microextraction　(EE-SPME)　technology.　Compared　to　the　powder　form,　F–COF@polyILs　coating　displays　effective　non-selective　large-size　molecular　sieving.　Combining　gas　chromatography-tandem　triple　quadrupole　mass　spectrometry　(GC-MS/MS),　we　have　established　a　simple,　efficient　quantitative　analysis　method　for　OH-PAHs　with　a　low　detection　limit　(0.008–0.05　ng　L−1),　wide　linear　range　(0.02–1000　ng　L−1),　and　good　repeatability　(1.0%–7.3　%).　Experimental　results　show　that　the　coated　fiber　exhibits　good　resistance　to　matrix　interference　(2.5%–16.7　%)　in　complex　biological　matrices,　and　has　been　successfully　used　for　OH-PAHs　analysis　in　human　urine　and　plasma.　Significance:　FW　technology　realizes　the　transformation　of　the　traditional　powder　form　of　COF　in　SPME　coating　to　a　uniform　non-powder　coating,　giving　its　ability　to　exclude　large　molecules　in　complex　biological　matrices.　A　method　for　quantitatively　detecting　OH-PAHs　in　real　biological　samples　was　also　developed.　Therefore,　the　filament　winding　preparation　method　for　F–COF@polyILs　coated　fibers,　along　with　fibrous　COFs＇　morphology　control,　has　substantial　implications　for　efficiently　extracting　target　compounds　from　complex　matrices.　©　2024　Elsevier　B.V.