The　immobilized　metal　ion　affinity　chromatography（IMAC）　theory　was　employed　to　design　and　synthesize　a　poly（VIM-co-DVB）-Cu2+　monolithic　column.　The　poly（VIM-co-DVB）　matrix　monolithic　column　was　initially　prepared　via　thermally　initiated　polymerization　of　1-vinylimidazole（VIM）　and　divinylbenzene（DVB），and　Cu2+　was　immobilized　directly　on　the　matrix　monolithic　column　through　a　post-modification　multi-step　method.　The　extraction　conditions　of　the　affinity　monolithic　columns　were　optimized.　Under　the　optimal　conditions，the　poly（VIM-co-DVB）-Cu2+　monolithic　column　was　applied　for　capillary　microextraction（CME）　of　microcystins（MCs）　prior　to　high　performance　liquid　chromatography-mass　spectrometry（HPLC-MS）　analysis　in　both　tap　water　and　lake　water　samples.　The　detection　limits　of　MCs　ranged　from　0.89　to　1.23　ng/L，with　recoveries　between　80.0%　and　105%，and　the　relative　standard　deviations（RSDs）　were　not　more　than　6.8%.　The　validated　CME/HPLC-MS　methodology　exhibits　exceptional　sensitivity　and　accuracy，making　it　a　valuable　tool　for　the　monitoring　and　analysis　of　MCs　in　environmental　waters.　©　2024,　China　Association　for　Instrumental　Analysis.　All　rights　reserved.