In order to validate different methods of measuring urinary catecholamines (norepinephrine, epinephrine and dopamine) in humans, methods based on separation of catecholamines using reversed-phase or cation-exchange high-performance liquid chromatography with electrochemical detection were compared with an autoanalyser-based fluorescence method. Different methods for pre-chromatography sample purification were also studied. For measurements of urinary catecholamines, the reversed-phase-based chromatographic techniques studied were found to give less reliable results than cation-exchange chromatography, even if one of them (Clin Rep Urine Catecholamine Kit) gave almost as precise estimates. The autoanalyser technique yielded good results. It is concluded that cation-exchange chromatography with an appropriate sample work-up procedure (a combination of organic solvent extraction and alumina adsorption) is a reliable and accurate method for analyses of urinary catecholamines.