The voltammetric characteristics of adenine and adenosine at a copper electrode were investigated in different supporting electrolytes. It was found that citric acid had some activating effect at the copper electrode and the oxidation reaction of adenine and adenosine at the copper electrode could be observed in the solution, if PO43−and citric acid exist simultaneously. The oxidation reaction of adenine and adenosine could be applied to capillary zone electrophoresis with end column amperometric detection for their determination. The method was applied to the determination of adenine in yeast-RNA.