We report on a method for the determination of the biogenic amines (BAs) spermine, spermidine, histamine, cadaverine, β-phenylethylamine, tyramine and tryptamine. It is based on capillary zone electrophoresis in the presence of 18-crown-6 (180 mM), and is making use of amperometric detection. Under optimized conditions, seven BAs could be well separated within 29 min at a separation voltage of 14 kV in a buffer solution of pH 3.6. The limits of detection for seven BAs are around 10 ng.mL −1 for standard mixtures. The method does not require preconcentration and derivatization steps, and thus provides an attractive alternative to quantitative multi-analysis of BAs in water samples.