Combining　free　radical　polymerization　with　click　chemistry　via　copper-mediated　azide-alkyne　cycloaddition　(CuAAC)　reaction　in　a　＂one-pot＂　process,　a　facile　approach　was　developed　for　the　preparation　of　a　polymer　monolithic　column　carrying　6-azidohexanoic　acid　(AHA),　which　was　applied　in　capillary　liquid　chromatography　(cLC)　separations　in　the　mixed-mode.　The　synthetic　procedure　was　simple,　time-saving　and　without　any　post　modification.　The　morphology,　permeability,　and　pore　properties　of　the　prepared　polymer　monolithic　columns　were　characterized　and　the　results　showed　the　polymer　monoliths　have　a　uniform　monolithic　structure　with　high　porosity.　The　retention　behavior　of　the　neutral　and　polar　solutes　on　the　polymer　monoliths　confirmed　the　successful　incorporation　of　ligand　in　the　monolithic　matrix.　A　series　of　alkylbenzenes,　phenols,　and　anilines　were　used　to　evaluate　the　chromatographic　properties　of　the　polymer　monolith　in　terms　of　hydrophobic,　hydrophilic　and　cation-exchange　interactions.　In　addition,　the　poly　(AHA-co-propargyl　methacrylate-co-ethylene　dimethacrylate)　(AHA-co-PMA-co-EDMA)　monolithic　column　could　be　successfully　applied　to　the　separation　of　polycyclic　aromatic　hydrocarbons　(PAHs),　nucleosides　and　nucleobases,　alkaloids,　peptides　and　proteins.　The　reproducibility　of　the　monolithic　column　was　less　than　4.0%　in　terms　of　relative　standard　deviation　(RSD)　of　the　retention　factor.　The　results　demonstrate　that　the　proposed　method　was　an　effective　alternative　for　the　preparation　of　the　polymer　monolith.　©　The　Royal　Society　of　Chemistry　2015.