Combining　free　radical　polymerization　with　click　chemistry　via　a　copper-mediated　azide/alkyne　cycloaddition　(CuAAC)　reaction　in　a　＂one-pot＂　process,　a　facile　approach　was　developed　for　the　preparation　of　a　poly(3′-azido-3′-deoxythymidine-co-propargyl　methacrylate-co-pentaerythritol　triacrylate)　(AZT-co-PMA-co-PETA)　monolithic　column.　The　resulting　poly(AZT-co-PMA-co-PETA)　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　a　monolithic　column.　A　series　of　alkylbenzenes,　amides,　anilines,　and　benzoic　acids　were　used　to　evaluate　the　chromatographic　properties　of　the　polymer　monolith　in　terms　of　hydrophobic,　hydrophilic　and　cation-exchange　interactions,　and　the　results　showed　that　the　poly(AZT-co-PMA-co-PETA)　monolith　exhibited　more　flexible　adjustment　in　chromatographic　selectivity　than　that　of　the　parent　poly(PMA-co-PETA)　and　AZT-modified　poly(PMA-co-PETA)　monoliths.　Column　efficiencies　for　toluene,　DMF,　and　formamide　with　35000-48000　theoretical　plates　per　m　could　be　obtained　at　a　linear　velocity　of　0.17　mm　s-1.　The　run-to-run,　column-to-column,　and　batch-to-batch　repeatabilities　of　the　retention　factors　were　less　than　4.2%.　In　addition,　the　proposed　monolith　was　also　applied　to　efficient　separation　of　sulfonamides,　nucleobases　and　nucleosides,　anesthetics　and　proteins　for　demonstrating　its　potential.　©　2015　The　Royal　Society　of　Chemistry.