An　ionic　liquid　hybrid　zwitterionic　polymer　capillary　microextraction　(CME)　column　was　prepared　for　the　biomimetic　enrichment　of　glycopeptides　by　one-step　copolymerization　of　2-methacryloyloxyethyl　phosphorylcholine　(MPC)　and　1-butyl-3-vinylimidazolium　bromide,　in　the　presence　of　crosslinker　trimethylolpropane　trimethacrylate　(TMA).　The　resultant　monolith　was　characterized　by　scanning　electron　microscopy　(SEM),　fourier　transform　infrared　(FT-IR)　spectroscopy　and　pore　size　distribution　measurement.　Due　to　the　incorporation　of　zwitterionic　MPC　owning　a　unique　biomimic　structure　(i.e.　hydrophilic　cation/anion　and　hydrophobic　long-alkyl　chain),　the　monolithic　column　has　large　pore　size　and　good　biocompatibility,　exhibiting　high　extraction　efficiency,　permeability　and　fast　mass　transfer　to　targets.　Besides,　the　use　of　ionic　liquids　(ILs)　as　co-monomer　in　the　polymerization　endows　the　monolith　with　enhanced　mechanical　stability,　uniformity　and　multiple　interactions.　The　prepared　column　was　successfully　applied　in　CME　coupled　to　capillary　electrochromatography　(CEC)　for　the　efficient　enrichment　and　separation　of　glycopeptide　antibiotics　in　foodstuff.　The　method　demonstrated　a　wide　linear　range　(50.0–18000.0　µg　L-1),　low　detection　limits　(5.0–10.0　µg　L-1,　S/N　=　3)　and　satisfied　recoveries　(76.0–109.7%).　This　work　shows　the　advantage　of　fine-tuning　biomimetic　monoliths　in　application-specific　CME–CEC.　©　2020　Elsevier　B.V.