A　simple,　rapid,　sensitive　and　specific　method　using　capillary　electrophoresis　(CE)　coupled　with　electrostacking　and　amperometric　detection　(AD)　has　been　developed　for　the　simultaneous　separation　and　determination　of　clenbuterol　(CLB),　terbutaline　(TER),　salbutamol　(SAL)　and　formoterol　(FMT).　In　this　paper,　the　CE　separation　and　AD　conditions　were　investigated　in　detail.　The　optimum　conditions　were:　pH　8.6　Na2B4O7-H3BO3　buffer　solution　(20.0　mmol/L),　9　kV　for　the　separation　voltage,　and　1000　mV　(versus　Ag/AgCl)　for　the　detection　potential.　When　the　sample　which　was　dissolved　in　70%　ACN-water　mixture　solution　was　injected　60　s　by　15　kV　electrokinetic　injection,　the　best　stacking　effects　was　obtained.　Under　the　optimum　conditions,　the　enhancement　factors　of　these　beta(2)-agonists　had　been　greatly　improved　more　than　5500-fold　compared　with　the　conventional　electrokinetic　injection.　And　then　an　excellent　linear　response　was　obtained　with　LODs　(S/N　=　3)　of　0.098,　0.024,　0.063　and　0.920　pmol/L　for　CLB,　TER,　SAL　and　FMT　in　urine,　respectively.　The　precision　weas　determined　in　both　intra-day　(n　=　5)　and　inter-day　(n　=　15)　assays,　and　the　RSDs　were　not　more　than　2.1　and　3.4%　for　migration　time　and　peak　current,　respectively.　The　proposed　method　has　been　applied　to　analyze　human　urine　samples　successfully.