Design　and　preparation　of　fiber　coatings　with　excellent　electrochemical　performance　and　high　polarity　is　significant　for　efficient　extraction　of　polar　targets　in　electro-enhanced　solid-phase　microextraction　(EE-SPME).　In　this　work,　a　combination　strategy　for　structure　regulation　of　covalent　organic　framework　(COF)　was　proposed　to　fabricate　a　nitrogen-rich　thiocarbamide　linked　COF　coating　(Thiocarbamide-TZ-DHTP)　via　molecular　design　and　post-synthetic　thiocarbamide　conversion.　The　prepared　COF　coating　possesses　a　large　number　of　O,　N,　and　S　functional　groups,　which　not　only　endow　the　coating　with　higher　polarity　but　also　significantly　enhance　its　electrochemical　performance.　The　COF　coating　was　used　for　EE-SPME　of　polar　bisphenols　(BPs),　demonstrating　excellent　enrichment　efficiency　and　durability.　Subsequently,　coupled　with　gas　chromatography-tandem　mass　spectrometry　(GC-MS/MS),　a　sensitive　method　was　developed　for　determination　of　trace　BPs.　The　established　method　possess　wide　linear　ranges　(2.0–800.0　ng　L−1),　good　correlation　coefficients　(0.9985–0.9994)　and　low　detection　limits　(0.1–2.0　ng　L−1).　Moreover,　the　established　method　had　been　successfully　applied　to　detection　of　trace　BPs　in　tea　beverage　with　satisfactory　recoveries　(81.6　%　to　118.6　%).　This　research　provides　a　feasible　pathway　for　preparing　COF　coating　with　excellent　electrochemical　performance　and　high　polarity　for　EE-SPME.　©　2024　Elsevier　B.V.