Using nonchiral high-performance liquid chromatography (HPLC) coupled with a circular dichroism (CD) detector, we developed a new method to determine the enantiomeric excess (e.e.) of glucose derivatized with chromophores (p-bromobenzoate). This method is suitable for microscale analysis of glycoside and saccharide. As an application of this method, the enantiomeric excess of the component glucose of a glucan was assayed.