A　simple　and　rapid　capillary　electrophoresis　(CE)　with　an　acidic　potassium　permanganate　chemiluminescence　(CL)　detection　method　was　developed　to　determine　three　alkaloids　(curine,　sinomenine　and　magnoflorine)　simultaneously.　A　laboratory-built　CE-CL　detection　interface　was　used.　The　field-amplified　sample　stacking　technique　was　applied　to　the　online　concentration　of　alkaloids.　Experimental　conditions　for　CE　separation　and　CL　detection　were　investigated　in　detail　to　acquire　optimum　conditions.　Under　optimal　conditions,　the　three　alkaloids　were　baseline　separated　within　6　min,　and　the　detection　limits　(S/N　=　3)　ranged　from　0.03　μg/mL　to　0.49　μg/mL.　This　method　was　successfully　applied　to　determine　the　above　three　alkaloids　in　Sinomenium　acutum,　and　the　result　of　the　determination　of　sinomenine　was　in　good　agreement　with　those　given　by　high-performance　liquid　chromatography　and　CE　methods.　In　addition,　a　possible　CL　reaction　mechanism　of　sinomenine-KMnO4-H　2SO4　was　proposed.　Copyright　©　2013　John　Wiley　&　Sons,　Ltd.　Copyright　©　2013　John　Wiley　&　Sons,　Ltd.