Capillary electrophoretic (CE) methods have been used to separate and determine a wide range of water-soluble vitamins in pharmaceutical preparations, but has found limited application in determining vitamins at naturally occurring levels in food and beverages. CE has been used to determine vitamin C in fruits and beverages, niacin in a range of foods and thiamine in samples of meat and milk. The CE methodologies used to determine vitamins in pharmaceutical preparations and biological fluids are also included as examples of the effectiveness of CE in vitamin analysis.