A　highly　sensitive　capillary　electrophoretic　profiling　of　nicotine　(NIC)　and　nornicotine　(NNIC)　was　developed　and　applied　to　mushrooms　with　amperometric　detection　(AD).　Effects　of　the　experimental　factors　including　detection　potential,　separation　parameters,　and　sample　pretreatment　conditions　were　investigated.　Under　the　optimal　conditions,　the　electrophoretic　analysis　of　NIC　and　NNIC　was　achieved　within　8　min　on　a　pencil　carbon　disc　working　electrode　at　0.95　V,　which　was　lower　than　those　reported　previously.　Good　calibration　curves　were　obtained　in　0.01-2.0　μg/mL　and　0.02-3.0　μg/mL　with　the　LOD　of　2　ng/mL　and　5　ng/mL　for　NIC　and　NNIC,　respectively.　The　feasibility　of　the　resultant　method　was　verified.　Average　recoveries　of　different　fortified　levels　ranged　in　80.7-86.0%　and　94.0-98.6%　for　NNIC　and　NIC　were　gained,　respectively.　Applied　to　a　range　of　mushrooms　(Boletus　edulis　and　Lentinus　edodes),　the　NIC　contained　naturally　was　successfully　found　in　the　level　of　19.71-79.20　μg/kg.　The　results　obtained　with　CE-AD　method　were　acceptable　and　close　to　that　of　HPLC-MS.　©　2013　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim.