A　new　polymer　monolith　with　three　modes　of　reverse-phase,　hydrophilic　and　cation-exchange　interaction　was　synthesized　in　100　mu　m　i.d.　fused-silica　capillary　by　in　situ　polymerization　procedure.　The　pre-polymerization　mixture　consisted　of　glycidyl　methacrylate　(GMA)　and　4-vinylphenylboronic　acid　(VPBA)　as　bifunctional　monomers,　ethylene　dimethacrylate　(EDMA)　as　crosslinker,　1,4-butanediol　(BDO)　and　diethylene　glycol　(DEG)　as　binary　porogenic　solvents,　and　azobisisobutyronitrile　(AIBN)　as　initiator.　The　resulting　poly(GMA-co-VPBA-co-EDMA)　monolith　showed　a　relatively　homogeneous　monolithic　structure,　good　permeability　and　mechanical　stability.　Different　ratios　of　monomers　and　porogens　were　used　for　optimizing　the　properties　of　monolithic　column.　The　column　performance　was　assessed　by　the　separation　of　a　series　of　neutral　solutes,　charge　solutes,　phenols　and　anilines.　Compared　with　poly(GMA-co-EDMA)　monolith,　the　proposed　monolith　exhibited　more　flexible　adjustment　of　selectivity　in　terms　of　hydrophobic,　hydrophilic,　as　well　as　cation-exchange　interaction　in　the　same　chromatographic　conditions.　High　column　efficiencies　for　benzene　derivatives　with　70,000-102,000　theoretical　plates/m　could　be　obtained　at　a　linear　velocity　of　0.265　mm/s.　The　run-to-run,　column-to-column,　and　batch-to-batch　repeatabilities　of　the　retention　times　were　less　than　8.23%.　Additionally,　the　purposed　monolith　was　also　applied　to　efficient　separation　of　alkaloids　and　proteins　for　demonstrating　its　potential　in　biomolecule　separation.　Crown　Copyright　(C)　2012　Published　by　Elsevier　B.V.　All　rights　reserved.