The　release　of　microcystin　(MCs)　in　aquatic　ecosystems　poses　a　substantial　risk　to　the　safety　of　irrigation　and　drinking　water.　In　view　of　the　challenges　associated　with　monitoring　MCs　in　water　bodies,　given　their　low　concentration　levels　(μg/L　to　ng/L)　and　the　presence　of　diverse　matrix　interferences,　there　is　an　urgent　need　to　develop　an　efficient,　cost-effective　and　selective　enrichment　technique　for　MCs　prior　to　its　quantification.　In　this　work,　a　gold　nanoparticles　(AuNPs)-functionalized　zwitterionic　polymer　monolith　was　described　and　further　applied　for　the　affinity　enrichment　of　MCs.　Monoliths　modified　with　zwitterionic　amino　acid　ligands　were　synthesized　within　capillary　microchannels　as　highly　permeable　porous　supports　for　the　immobilization　of　gold　nanoparticles　via　electrostatic　interactions.　The　structure　and　morphology　of　AuNPs-hybrid　monoliths　were　characterized　by　X-ray　diffraction　(XRD),　scanning　electron　microscopy　(SEM)　and　FT-IR　spectroscopy,　confirming　the　uniform　loading　of　AuNPs　on　the　polymer　matrix　while　ensuring　porous　structural　stability.　The　as-prepared　hybrid　monolith　was　employed　as　a　sorbent　for　capillary　microextraction　(CME)　prior　to　liquid　chromatography-mass　spectrometry　(LC-MS)　analysis.　The　results　demonstrated　that　the　functionalization　of　AuNPs　under　the　protection　of　zwitterionic　polymers　markedly　enhanced　the　extraction　ability　of　the　monolithic　column　for　MCs.　This　is　attributed　to　the　formation　of　ligand　exchange,　hydrophobic　interactions,　and　π-system　interactions　between　MCs　and　AuNPs,　as　verified　by　zeta　potential　and　XPS　characterization.　The　developed　CME-LC-MS　method　exhibited　a　wide　linear　range　(1–10,000　ng　L−1),　a　low　limit　of　detection　(0.58–1.6　ng　L−1),　and　satisfactory　recoveries　(71.0–126.7　%)　for　three　MCs　in　different　ambient　water　sample　matrices.　It　is　evident　from　these　findings　that　AuNPs-functionalized　zwitterionic　polymers　represent　a　promising　novel　material　for　the　efficient　adsorption　of　MCs　from　aqueous　samples.　©　2024　Elsevier　B.V.