A simple and reproducible method, based on micellar electrokinetic capillary chromatography (MECC) with amperometric detection (AD), for the separation and determination of the biogenic amines and their precursor amino acids was studied in this paper. The optimal conditions of separation and detection of typtamine, tyramine, tryptophan and tyrosine were 0.020 mol l-1borate-NaOH (pH10.35) containing 0.03 mol l-1 sodium dodecylsulphate (SDS) as running buffer, 20kV as separation voltage, and+800mV (vs. SCE) as detection potential. Under the optimum conditions, the four analytes were separated completely within 15 minutes, and good linearity, reproducibility and recovery results were obtained. Based on three times standard deviation of a low level sample, the detection limits for the four analytes were as low as at 10-7 mol l-1 level. This method was also successfully used in the analysis of actual rice spirit, and satisfactory assay results were obtained.