Conductive　covalent　organic　frameworks　(COFs)　have　received　considerable　attention　and　are　critical　in　various　applications　such　as　electro-enhanced　solid-phase　microextraction　(EE-SPME).　In　this　work,　a　novel　piperazine-linked　copper-doped　phthalocyanine　metal　covalent　organic　framework　(CuPc-MCOF)　was　synthesized　with　good　stability　and　high　electrical　conductivity.　The　synthesized　CuPc-MCOF　was　then　used　as　an　EE-SPME　coating　material　for　extraction　of　five　trace　chlorophenols　(CPs),　including　2,4-dichlorophenol　(2,4-DCP),　2,6-dichlorophenol　(2,6-DCP),　2,4,6-trichlorophenol　(2,4,6-TCP),　2,4,5-trichlorophenol　(2,4,5-TCP)　and　2,4,5,6-tetrachlorophenol　(2,4,5,6-TCP),　exhibiting　excellent　extraction　performance　because　of　various　synergistic　forces　between　CuPc-MCOF　fibers　and　CPs.　By　combining　EE-SPME　with　gas　chromatography-tandem　mass　spectrometry　(GC–MS/MS),　a　sensitive　method　for　CPs　detection　was　established　with　a　low　limit　of　detection　(0.8–5　ng　L−1)　and　good　reproducibility　(RSD≤8.4%,　n　=　3).　This　method　was　then　successfully　applied　to　the　analysis　of　trace　CPs　in　real　samples　of　seawater　and　seafood.　Results　showed　that　the　developed　CuPc-MCOF　coating　material　possessed　superior　extraction　performance　and　potential　application　in　extraction　of　trace　polar　pollutants　from　complex　samples.　©　2023　Elsevier　B.V.