An overview of the application of capillary electrophoresis and capillary electrophoresis–mass spectrometry in the analysis of simple carbohydrates without any previous derivatization step is given. Besides electrolyte systems for carbohydrate separation, detection techniques employed in capillary electrophoresis, such as spectrophotometric detection, electrochemical detection, and mass spectrometric detection, are discussed, as are less common detection techniques. Thus, the chapter focuses on the assessment of the strong and weak points of these detection techniques for carbohydrate analysis. A table included in this chapter gives a comprehensive listing of capillary electrophoresis and capillary electrophoresis–mass spectrometry applications in the fields of carbohydrate analysis published within the last decade.