The　functionalization　of　covalent　organic　frameworks　(COFs)　identifies　significant　potential　for　developing　selective　coating　materials　for　solid-phase　microextraction　(SPME).　Herein,　a　chlorine-functionalized　covalent　organic　framework　(CF–COF)　was　in-situ　synthesized　by　employing　triformylphloroglucinol　(Tp)　and　2,5-dichloro-1,4-phenylenediamine　(2,5-DCA)　as　monomers　on　an　amino-functionalized　stainless　steel　wire.　The　obtained　CF-COF　coated　fiber　exhibited　a　higher　enrichment　capacity　for　polychlorinated　biphenyls　(PCBs)　than　commercial　fibers　and　non-chlorinated　COF　fiber,　owing　to　a　more　hydrophobic　surface,　size-matching　effect,　a　large　number　of　micropores　and　the　π–π　stacking　interactions　between　COF　coating　and　analytes.　As　a　practical　application,　the　CF-COF　coated　fiber　was　applied　to　the　headspace　extraction　of　17　PCBs　prior　to　their　quantification　by　GC/MS.　The　established　analytical　method　offered　a　good　linearity　in　the　range　of　0.1–1000　ng　L−1,　low　detection　limits　of　0.0015–0.0088　ng　L−1,　and　satisfactory　enhancement　factors　(EFs)　of　699–4281.　The　repeatability　for　single　fiber　and　the　fiber-to-fiber　reproducibility　was　lower　than　9.26%　and　9.33%,　respectively.　The　proposed　method　was　verified　to　be　sensitive,　selective,　and　applicable　for　the　analysis　of　ultra-trace　PCBs　in　environmental　surface　water　samples　with　the　recoveries　ranged　from　78.7%　to　124.0%.　©　2021　Elsevier　B.V.