Fabricating　functional　electrospun　nanofiber　coating　for　highly　selective　extraction　of　microcystin-LR　(MC-LR)　was　of　significant　importance　for　water-safety　monitoring.　Herein,　a　novel　MOF@aptamer　functionalized　nanofabric　was　presented　via　a　facile　and　reliable　strategy　integrating　polydopamine　(PDA)　mediation　and　thiol-ene　chemistry　and　applied　for　specific　recognition　of　the　MC-LR　model　analyte.　Using　polydopamine　(PDA)　as　the　mediating　layer,　vinyl-UiO-66　MOF　was　grown　in　situ,　followed　by　post-synthetic　modification　(PSM)　of　Zr4+　with　vinyl　phosphate　and　rapid　UV-initiated　click　reaction　of　aptamers.　Uniform　deposition　of　Zr-based　MOF　(vinyl-UiO-66)　on　the　nanofibers　was　directly　produced,　and　the　tedious　co-electrospinning　process　was　abandoned　to　prevent　the　aggregation　and　encapsulation　of　MOF.　Via　an　efficient　“thiol-ene”　chemistry,　massive　thiol-terminated　aptamers　were　grafted　on　MOF　within　one　step　under　friendly　conditions,　rather　than　the　time-consuming　nanoparticle　adsorption　or　unfriendly　covalent　chemical　reactions.　As　a　result,　the　robust　MOF@aptamer-coated　nano-fabrics　were　obtained,　and　a　highly　selective　performance　towards　MC-LR　was　illustrated　with　a　limit　of　detection　(LOD)　at　0.002　ng/mL,　good　precision　(CV<8.3%),　good　repeatability　(2.2∼6.0%)　when　coupled　with　LC-MS.　Almost　1∼2　orders　of　magnitude　higher　detection　sensitivity　was　exhibited　than　that　of　the　common　non-specific　SPE/SPME　fiber　reported　so　far.　Applied　to　water　samples,　the　good　matrix-resistance　ability,　and　acceptable　recovery　yields　were　achieved　with　high　specificity.　This　strategy　might　provide　a　rapid　and　friendly　protocol　to　efficiently　fabricate　MOF@aptamer　functionalized　nano-fabrics　through　electrospinning　and　interfacial　＂thiol-ene＂　chemistry　for　highly-selective　microextraction.　©　2022