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A rapid and sensitive method for the analysis of three catecholamines by capillary electrophoresis (CE) with direct chemiluminescence (CL) detection is described. The detection limits (S/N = 3) were 1.3 × 10-8 g/mL for isoprenaline,1.0 × 10-8 g/mL for epinephrine and 2.8 × 10-8 g/mL for dopamine. The proposed method was successfully applied to the analysis of catecholamines in urine samples of cigarette smokers and nonsmokers. The results showed that there is a close relation between the release of dopamine in human body fluids and cigarette smoking/nonsmoking.