A capillary electrophoresis-mass spectrometry method for the simultaneous chiral determination of enantiomers of methamphetamine (MA), amphetamine (AP), dimethylamphetamine (DMA) and p-hydroxymethamphetamine (pOHMA), in urine has been developed. The internal standards used were 2-phenylethylamine and 1-amino4-phenylbutane. The electrolyte was 1 M formic acid (pH 2.2). The chiral selector, which was added to the electrolyte, was a mixture of 3 mM beta-cyclodextrin and 10 mM heptakis(2,6-di-O-methyl)-beta-cyclodextrin. The detection limits were 0.03 microg ml(-1) for the enantiomers of MA and AP and 0.05 microg ml(-1) for the enantiomers of pOHMA using selected ion monitoring. In the analysis of healthy adult urine samples spiked with MA, AP and pOHMA, the precision of within-run assays (n = 4) for the migration time after correction with two internal standards were under 0.04%, and the detection yields utilizing solid phase extraction were 95-105%. This method was applicable to the analysis of urine samples of MA addicts and DMA addicts.