Efficient　separation　of　alkaloid　from　the　extract　of　traditional　Chinese　medicine　(TCM)　provides　a　valuable　means　to　advance　modernization　of　TCM.　Herein,　we　proposed　an　electrodialysis　(ED)　process　to　efficiently　separate　the　positively　charged　alkaloid　(synephrine+　as　a　case)　from　the　extract　of　TCM　that　contains　synephrine+　and　naringin　(naringin±,　naringin−,　or　naringin2−).　Results　indicated　that　the　concentration　polarization　occurred　at　the　surfaces　of　both　anion　exchange　membrane　(CP@AEM)　and　cation　exchange　membrane　(CP@CEM)　during　the　constant-voltage　ED　process.　Furthermore,　a　high　stack　voltage　can　result　in　a　more　intensive　CP@AEM　compared　with　CP@CEM,　resulting　in　the　competitive　migration　of　H+　with　synephrine+　through　the　CEM,　thus　a　decreased　current　efficiency.　Nevertheless,　a　high　flux　and　recovery　rate　of　synephrine+　can　be　obtained　at　a　high　stack　voltage.　In　addition,　a　high　feed　concentration　can　result　in　a　high　current　density　and　flux　as　well　as　high　treatment　capacity,　and　thus　a　low　capital　expenditure.　At　the　optimized　conditions,　a　high　flux　(1.546　mol　m−2　h−1),　high　recovery　rate　(88.05　%),　relatively　high　current　efficiency　(84.57　%),　and　a　low　total　cost　(0.969　$　kg−1)　can　be　obtained,　and　no　naringin　leakage　was　found.　Notably,　the　obtained　flux　is　three　orders　of　magnitude　of　the　flux　of　the　similar　molecular　weight　organic　substance　separated　by　nanofiltration.　In　addition,　the　continuous　ten-cycle　operation　featured　a　preponderant　long-term　stability　of　ED　process　due　to　the　stable　separation　performance　and　negligible　membrane　fouling.　These　findings　suggest　that　ED　is　a　promising　method　to　efficiently　separate　alkaloid　from　the　extract　of　TCM.　©　2025　Elsevier　B.V.