To routinely assay the flavin contents in foodstuffs, a rapid and sensitive method was developed, in which the powerful separation capabilities of high-performance capillary electrophoresis (CE) were exploited. The method is based on a simple sample preparation, electrophoretic separation and laser induced fluorescence (LIF) detection. The average content of water-soluble riboflavin vitamers in raw natural products (i.e. vegetables, wheat flours and tomatoes) and baker's yeasts was evaluated without interferences from the sample matrices. Such an accurate and highly sensitive CE-LIF technique represents a significant improvement over previous analytical methods in terms of sensitivity, simplicity and efficiency. Indeed, it is well suited to satisfy the demands for accurate and sensitive detection with minimal sample preparation and clean-up. (C) 2003 Elsevier Science Ltd. All rights reserved.