As a group of very important components in herbal drugs, carbohydrates analyses have gained increasing interest in the past decade. In this chapter, a brief description of herbal carbohydrates is presented, including the classification and pharmacological activities of mono-, oligo- and polysaccharides, and glycoconjugates such as glycopeptides and glycoproteins, glycosaminoglycans, and glycolipids. Next, sample preparation techniques such as extraction, purification, hydrolysis, and derivatization are discussed. Subsequently, separation and detection by capillary electrophoresis (CE) is reviewed. Finally, the applications of CE to the analysis of herbal carbohydrates are summarized. This chapter provides a reference for further applications of CE in this field.