OBJECTIVE: To establish and validate the method for the determination of carbamazepine (CBZ) in human plasma, and to apply the method for external quality assessment. METHODS: After precipitated with acetonitrile, the plasma sample was determined by LC-MS/MS. Using loratadine as internal standard, the determination was performed on Kromasil C18 column with mobile phase consisted of water (containing 0.1% formic acid)-acetonitrile (gradient elution) at flow rate of 0.6 ml/min and column temperature of 40 ℃. The ion transitions under MRM mode by ESI+ ionization were performed at m/z 237.1→194.0 and m/z 383.1→267.0 for CBZ and internal standard, respectively. RESULTS: The linear range of CBZ were 5-1 000 ng/ml (r>0.998). The limit of quantitation was 5 ng/ml. RSDs of inter-day and intra-day were 1.00%-6.42%; relative deviation were -6.93%-0.32%. The external quality assessment of 5 samples were 679.0, 475.0, 104.0, 29.2 and 26.2 ng/ml, respectively. The pass rate of assessment result was 100%. CONCLUSIONS: The method is sensitive, accurate and specific. The method is applicable for the plasma concentration determination and external quality assessment of CBZ.