To　capture　fluoroquinolones　(FQs)　from　complex　samples　efficiently,　a　new　hybrid　metal–organic　framework　(MOF)@monolith　material　(HMM)　was　fabricated　and　employed　as　the　extraction　medium　of　multi-monolith　fibers　solid　phase　microextraction　(MMF-SPME).　Porous　monolithic　fibers　based　on　allyltrimethylammonium　chloride-co-ethylene　glycol　dimethacrylate/divinylbenzene　polymer　were　fabricated　firstly.　After　that,　the　strategy　of　layer-by-layer　self-assembly　was　employed　to　prepare　zeolitic　imidazolate　frameworks　within　the　pores　and　the　surface　of　the　monolith.　Various　characterization　results　well　evidenced　that　the　introduction　of　MOF　not　only　enhanced　the　surface　area　of　adsorbent,　but　also　introduced　new　active　sites.　The　prepared　HMM/MMF-SPME　presented　satisfactory　capture　performance　towards　studied　FQs　by　multiple　interactions.　Enrichment　factors　of　FQs　in　human　urine　and　milk　samples　were　in　the　ranges　of　99–128　and　85–121,　respectively.　Under　the　most　beneficial　fabrication　and　extraction　parameters,　HMM/MMF-SPME　was　combined　with　high-performance　liquid　chromatography　to　quantify　trace　FQs　in　urine　and　milk　samples.　High　sensitivity　(limits　of　detection　were　0.0072–0.031　μg/L　for　urine　sample　and　0.016–0.057　μg/kg　for　milk　sample)　and　good　precision　(RSDs　below　10%)　were　obtained.　In　the　analysis　of　FQs　in　actual　samples,　the　recovery　at　different　spiked　contents　varied　from　77.4%　to　120%,　with　good　reproducibility.　Accuracy　and　reliability　of　established　approach　were　well　verified　with　confirmation　experiments.　Satisfactory　results　evidence　that　the　developed　HMM/MMF-SPME　can　be　a　prominent　technique　for　the　capture　of　trace　FQs　in　complex　samples.　©　2023　Elsevier　B.V.