The chiral separation of catecholamines and structurally related compounds was achieved by capillary electrophoresis in the reversed-polarity mode (RP).The RP mode was conducted employing 100 mM neutral heptakis(2,6-di-O-methyl)-β-cyclodextrin as the chiral selector dissolved in the buffer (pH 3.0) containing hexadimethrine bromide (0.01%) as the electroosmotic flow reversing agent.In this result, fairly good enantiomeric resolutions were achieved.Relative migration times to that of internal standard under the respective optimum conditions were characteristic of each enantiomer with good precision.The method linearity and accuracy were found to be adequate for the chiral assay of the catecholamines and structurally related compounds investigated.Its applications to urine specimens from patients with cancer under treatment will be demonstrated.