Allyl‐β‐CD　was　synthesized　and　used　as　the　chiral　functional　monomer　to　prepare　chiral　organic　polymer　monolithic　columns　in　capillary　HPLC.　First,　the　enantioselectivity　of　the　prepared　allyl‐β‐CD　modified　organic　polymer　monolithic　capillary　columns　was　investigated.　Then,　the　influences　of　enantioseparation　conditions　of　chiral　drugs　were　further　explored.　Finally,　the　recognition　mechanism　was　studied　by　molecular　docking　with　AutoDock.　Complete　enantioseparations　of　four　chiral　drugs　as　well　as　partial　enantioseparations　of　eight　chiral　drugs　have　been　achieved.　Results　showed　that　the　RSD　values　for　run‐to‐run,　day‐to‐day,　and　column‐to‐column　variations　ranged　from　1.2%　to　4.6%,　1.4%　to　4.7%,　and　2.0%　to　6.1%,　respectively.　The　enantioselectivity　factor　rather　than　resolution　is　correlated　with　the　binding　free　energy　difference　between　enantiomers　with　allyl‐β‐CD.　Furthermore,　the　abundant　ether　bonds,　hydroxyl　groups,　and　hydrophobic　cavities　in　cyclodextrin　are　responsible　for　the　enantioseparation　ability　of　the　chiral　monolithic　capillary　columns.