A　capillary　electrophoresis　method　using　carboxymethyl-β-cyclodextrin　as　the　chiral　selector　and　mixture　of　methanol　and　ethanol　as　the　organic　additive　was　successfully　developed　for　the　simultaneous　enantioseparation　and　determination　of　six　β-blockers,　namely,　carteolol,　atenolol,　sotalol,　metoprolol,　esmolol　and　propranolol　in　this　paper.　The　most　suitable　running　buffer　for　enantioseparation　was　found　to　be　the　solution　of　20　mmol/L　NaH2PO4-Na2HOP4　(pH　5.5)　containing　1.5%w/v　carboxymethyl-β-cyclodextrin,　5%v/v　methanol　and　5%v/　v　ethanol.　Furthermore,　field-amplified　sample　injection　as　an　on-line　sample　stacking　method　was　developed　in　order　to　increase　the　detection　sensitivity.　The　experimental　conditions　for　both　simultaneous　enantioseparation　and　the　field-amplified　sample　injection　method　had　been　investigated　in　detail.　Under　the　optimum　conditions,　the　detection　limits　(defined　as　S/N　=　3)　of　this　method　were　0.01,　0.05,　0.05,　0.05,　0.05　and　0.5　μg/mL　for　(±)　carteolol,　(±)　atenolol,　(±)　sotalol,　(±)　metoprolol,　(±)　esmolol　and　(±)　propranolol,　respectively,　which　were　much　lower　than　those　of　the　conventional　methods.　The　enhancement　factors　were　greatly　improved　by　25-fold　for　the　enantiomers　of　the　β-blockers　except　five-fold　for　(±)　propranolol.　Eventually,　the　proposed　method　has　been　applied　for　the　analysis　of　human　serum　sample.　©　2008　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.