A　system　of　off-column　coaxial　flow　chemiluminescence　(CL)　detection　coupled　to　pressurized　CEC　(pCEC)　was　described.　The　interface　utilized　a　reactor　that　introduced　post-column　CL　reagent　into　the　capillary　effluents　in　a　sheathing　flow　profile.　To　compare　and　evaluate　band　broadening　of　analytes　caused　by　the　detector,　the　typical　CL　compounds　luminol　and　N-(4-aminobutyl)-N-ethylisoluminol　(ABEI)　were　separated　and　detected　by　pCEC　or　capillary　HPLC　(cHPLC)　coupled　to　CL　and　UV　detector,　respectively.　The　results　demonstrated　that　the　band　broadening　caused　by　off-column　detection　interface　was　minimized　due　to　the　fast　kinetic　nature　of　the　CL　reaction.　With　the　proposed　pCEC-CL　system,　the　detection　limits　of　luminol　and　ABEI　were　1.0　×　10-8　and　8.0　×　10-8　mol/L,　respectively,　which　were　approximately　100-fold　more　sensitive　than　those　obtained　with　UV　absorption.　In　addition,　separation　and　detection　of　the　ABEI-labeled　L-lysine　(L-Lys)　and　L-arginine　(L-Arg)　were　accomplished　by　pCEC-CL　method　based　on　the　principle　of　ABEI-potassium　ferricyanide-alkaline　medium　CL　reaction　system.　Under　the　optimum　conditions,　good　results　could　be　achieved　compared　with　pCEC-UV.　©　2008　Wiley-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.