Capillary electrophoresis combined with electrochemical detection at copper electrodes has been shown to provide a simple and sensitive method for the direct analysis of samples containing a wide range of carbohydrate compounds including simple sugars, sugar acids and alditols. In this approach, both the separation and the detection required the use of a strongly alkaline medium whose hydroxide content could be varied to optimize conveniently the migration times and resolution obtained. Detection consisted of a direct oxidation that required no derivatization and yielded detection limits at or below the fmol level for most of the carbohydrate species.