A　simple　and　sensitive　method　based　on　capillary　electrophoresis　(CE)　with　acidic　potassium　permanganate　chemiluminescence　(CL)　detection　has　been　developed　for　the　simultaneous　determination　of　three　alkaloids　(berberine,　palmatine　and　jatrorrhizine)　in　Rhizoma　coptidis.　A　lab-built　temperature-controlled　interface　was　used　for　the　CL　detection.　Experimental　conditions　for　CE　separation　and　CL　detection　were　investigated　in　detail　to　acquire　the　optimum　conditions.　The　optimized　condition　for　CL　detection　was　3.0　×　10sup-4/sup　M　potassium　permanganate　in　3.0　M　sulfuric　acid　solution　injected　by　a　microinjection　pump.　With　60　mM　phosphate　buffer　saline　(pH　=　8.0)-50%　(v/v)　methanol　buffer　as　the　running　buffer,　the　three　alkaloids　were　baseline　separated　within　13　min　at　a　separation　voltage　of　18　kV.　The　calibration　curves　exhibit　excellent　linearity　with　the　detection　limits　ranging　from　0.81　to　4.11　μg　mLsup-1/sup　for　the　three　alkaloids.　This　method　was　applied　for　the　determination　of　the　abovementioned　three　alkaloids　in　Rhizoma　coptidis　with　simple　extraction　procedures,　and　the　assay　results　were　satisfactory.　©　2015　The　Royal　Society　of　Chemistry.