A　simple　“one-pot”　approach　for　the　preparation　of　a　new　vinyl-functionalized　organic–inorganic　hybrid　monolithic　column　is　described.　In　this　improved　method,　the　hydrolyzed　alkoxysilanes　of　tetramethoxysilane　and　triethoxyvinylsilane　were　used　as　precursors　for　the　synthesis　of　a　silica-based　monolith,　while　1-hexadecene　and　sodium　ethylenesulfonate　were　used　as　vinyl　functional　monomers　along　with　azobisisobutyronitrile　as　an　initiator.　The　effects　of　reaction　temperature,　urea　content,　and　composition　of　organic　monomers　on　the　column　properties　(e.g.　morphology,　mechanical　stability,　and　chromatographic　performance)　were　investigated.　The　monolithic　column　was　used　for　the　separation　of　neutral　solutes　by　reversed-phase　pressurized　capillary.　Furthermore,　the　monolith　can　separate　various　aromatic　amines,　which　indicated　its　excellent　cation-exchange　capability　and　hydrophobic　interactions.　The　baseline　separation　of　the　aromatic　amines　was　obtained　with　a　column　efficiency　of　up　to　78 000　plates/m.　©　2017　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim