Enrichment　of　perfluoroalkyl　phosphonic　acids　(PFPAs)　is　of　great　significance　and　challenging　for　environmental　monitoring,　due　to　their　toxic　and　persistent　nature,　highly　fluorinated　character　as　well　as　low　concentration.　Herein,　novel　metal-organic　frameworks　(MOFs)　hybrid　monolithic　composites　were　prepared　via　metal　oxide-mediated　in　situ　growth　strategy　and　utilized　for　capillary　microextraction　(CME)　of　PFPAs.　A　porous　pristine　monolith　was　initially　obtained　by　copolymerization　of　the　zinc　oxide　nanoparticles　(ZnO-NPs)-dispersed　methacrylic　acid　(MAA)　with　ethylenedimethacrylate　(EDMA)　and　dodecafluoroheptyl　acrylate　(DFA).　Afterwards,　nanoscale-facilitated　transformation　of　ZnO　nanocrystals　into　the　zeolitic　imidazolate　framework-8　(ZIF-8)　nanocrystals　was　successfully　realized　via　the　dissolution-precipitation　of　the　embedded　ZnO-NPs　in　the　precursor　monolith　in　the　presence　of　2-methylimidazole.　Experimental　and　spectroscopic　results　(SEM,　N2　adsorption-desorption,　FT-IR,　XPS)　revealed　that　the　coating　of　ZIF-8　nanocrystals　significantly　increased　the　surface　area　of　the　obtained　ZIF-8　hybrid　monolith　and　endowed　the　material　abundant　surface-localized　unsaturated　zinc　sites.　The　proposed　adsorbent　showed　highly　enhanced　extraction　performance　for　PFPAs　in　CME,　which　was　mainly　ascribed　to　the　strong　fluorine　affinity,　Lewis　acid/base　complexing,　anion-exchange,　and　weakly　π-CF　interaction.　The　coupling　of　CME　with　LC-MS　enables　effective　and　sensitive　analysis　of　ultra-trace　PFPAs　in　environment　water　and　human　serum.　The　coupling　method　demonstrated　low　detection　limits　(2.16–4.12　ng　L−1)　with　satisfactory　recoveries　(82.0–108.0%)　and　precision　(RSDs　≤6.2%).　This　work　offered　a　versatile　route　to　design　and　fabricate　selective　materials　for　emerging　contaminant　enrichment　in　complicated　matrices.　©　2023　Elsevier　B.V.