A　new　method　for　pressurized　capillary　electrochromatography　(pCEC)　coupling　with　chemiluminescence　(CL)　detection　using　a　modified　on-column　coaxial　flow　detection　interface　was　developed.　To　evaluate　the　feasibility　and　reliability　of　the　experimental　setup,　the　typical　CL　compounds　luminol　and　isoluminol　were　separated　and　detected　by　using　this　pCEC-CL　system.　A　detailed　investigation　of　CL　detection　interface　and　postcolumn　CL　reagent　flow　rate　parameters　was　described.　The　excellent　resolution　and　detection　sensitivity　was　achieved　by　using　3-mu　m　ODS-C18　packed　column　with　30%　ACN　(v/v),　5　mmol/L　phosphate　buffer　(　pH　8.0).　Moreover,　with　the　presence　of　Co(II)　(1.0　x　10(-4)　mol/L)　in　the　mobile　phase,　the　linear　range　of　the　concentration　for　luminol　was　2.0　x　10(-9)-　2.0　x　10(-6)　mol/L　with　a　detection　limit　(S/N　=　3)　of　2.0　x　10(-10)　mol/L,　and　2.5　x　10(4)　theoretical　plates　was　achieved.　In　addition,　separation　and　detection　of　the　underivatized　amino　acids　(L-threonine　and　L-tyrosine)　were　accomplished　by　using　a　polymerized　monolithic　column　based　on　the　principle　of　the　luminol-H2O2-Cu(　II)-　amino　acid　CL　system.　Under　the　optimum　conditions,　the　mixture　of　amino　acids　was　efficiently　separated　with　satisfactory　results.