A　phenylboronic　acid-silica　hybrid　monolithic　column　for　capillary　liquid　chromatography　(cLC)　was　prepared　through　one-pot　process　by　using　4-vinylphenylboronic　acid　(VPBA)　and　alkoxysilanes　simultaneously.　The　effects　of　the　molar　ratio　of　tetramethyloxysilane/γ-methacryloxypropyltrimethoxysilane　(TMOS/γ-MAPS),　amount　of　VPBA,　and　the　volume　of　diethylene　glycol　(DEG)　on　the　morphologies,　permeabilities　and　pore　properties　of　the　prepared　VPBA-silica　hybrid　monolithic　columns　were　studied　in　detail.　A　relatively　uniform　monolithic　structure　with　high　porosity　was　obtained　with　optimized　ingredients.　A　series　of　cis-diol-containing　compounds,　alkylbenzenes,　amides,　and　anilines　were　utilized　to　evaluate　the　retention　behaviors　of　the　VPBA-silica　hybrid　monolithic　column.　The　result　demonstrated　that　the　prepared　VPBA-silica　hybrid　monolithic　column　exhibited　multiple　interactions　including　hydrophobicity,　hydrophilicity,　as　well　as　cation　exchange　apart　from　the　expected　affinity　interaction.　The　run-to-run,　column-to-column　and　batch-to-batch　reproducibility　of　the　VPBA-silica　hybrid　monolith　were　satisfactory　with　the　relative　standard　deviations　(RSDs)　less　than　1.63%　(n=5),　2.02%　(n=3)　and　2.90%　(n=5),　respectively,　indicating　the　effectiveness　and　practicability　of　the　proposed　method.　In　addition,　the　VPBA-silica　hybrid　monolithic　column　was　further　applied　to　the　separation　of　proteins　and　tryptic　digest　of　bovine　serum　albumin　(BSA),　respectively.　The　successful　applications　suggested　the　potential　of　the　VPBA-silica　hybrid　monolith　in　proteome　analysis.　©　2012　Elsevier　B.V.