In　this　work,　a　histidine-tagged　hexapeptide　functionalized　monolithic　material　is　described　for　the　efficient　capillary　microextraction　(CME)　of　microcystins　(MCs)　from　environment　waters.　1-Vinylimidazole　(VIM)　monomer　was　utilized　to　synthesize　the　matrix　polymer　monolith　by　the　copolymerization　with　divinylbenzene　(DVB)　crosslinker　in　the　presence　of　radical　initiator　azobisisobutyronitrile　(AIBN).　The　affinity　sorbent　was　then　prepared　by　a　metal　ion　chelation-based　multi-step　approach,　in　which　the　histidine　tag　peptide　Trp-His-Trp-LeuGln-Trp　(WHWLQW)　was　functionalized　on　a　Cu2+　modified　polymer　monolith　via　a　chelation　reaction　between　the　imidazole　group　of　histidine　and　Cu2+.　The　resultant　WHWLQW　functionalized　monolithic　material　had　high　affinity,　hierarchical　porosity　and　good　mechanical　stability.　Especially,　it　exhibited　favorable　enrichment　capacity　for　MCs　compared　to　other　affinity　materials　as　previously　reported.　With　the　optimized　CME　protocol,　MCs　at　ultra-trace　level　can　be　analyzed　by　CME　coupled　to　high　performance　liquid　chromatography-mass　spectrometry　(HPLC-MS)　in　different　aqueous　environmental　matrices.　The　average　recoveries　were　ranged　from　89.3%　to　104.5%　with　relative　standard　deviations　(RSD%)　of　2.1-8.4,　demonstrating　high　extraction　efficiency　and　repeatability.　The　limits　of　detection　(LODs)　of　MCs　were　determined　to　be　0.28-0.45　ng　L-1.　This　novel　biomimetic　sorbent　shows　promising　potential　for　the　enrichment　of　ultra-trace　pollutants　in　environment　waters.