A　mixed-mode　monolithic　stationary　phase　was　prepared　for　capillary　liquid　chromatography　(cLC)　by　in　situ　copolymerization　of　4-vinylphenylboronic　acid　(VPBA)　and　pentaerythritol　triacrylate　(PETA)　in　a　binary　porogenic　solvent　consisting　of　ethylene　glycol/cyclohexanol.　The　monomer　of　VPBA　functioned　as　ion-exchange　sites,　hydrophilic　ligands,　hydrophobic　groups　and　affinity　sites,　while　PETA　was　introduced　as　a　hydrophilic　crosslinker.　The　resultant　monoliths　with　different　column　properties　(e.g.　morphology,　permeability　and　selectivity)　were　optimized　by　adjusting　the　ratio　of　VPBA　to　PETA　and　the　composition　of　porogenic　solvent.　The　results　showed　that　the　selectivity　of　the　monoliths　increased　with　increasing　content　of　VPBA　in　the　polymerization　mixture.　A　series　of　alkylbenzenes,　amides,　and　anilines　were　used　to　evaluate　the　column　performance　in　terms　of　hydrophobic,　hydrophilic　and　cation-exchange　interactions.　At　an　optimized　flow　rate　of　50μL/min　(corresponding　to　0.265.　mm/s),　the　monolith　exhibited　high　column　efficiencies　of　43,000-100,000.　plates/m　for　alkylbenzenes.　Good　repeatability　was　obtained　with　relative　standard　deviation　(RSD)　of　retention　factor　(k)　less　than　0.65%　for　run-to-run　(n=5)　and　less　than　2.49%　for　column-to-column　(n=5).　In　addition,　the　poly(VPBA-co-PETA)　monolithic　column　was　applied　to　the　separation　of　phenols,　nucleobases,　and　proteins,　respectively.　These　successful　applications　demonstrate　the　purposed　monoliths　are　promising　for　cLC　separation　of　small　molecules　and　proteins.　©　2012　Elsevier　B.V.