Carbohydrates are widely distributed in nature and have multilateral functions. Recently glycobiology has evoked from the special interest in diverse functions of carbohydrates covalently bound to proteins and lipids. It has been revealed that the carbohydrate chains in such glycoconjugatges on cell surface are deeply associated with various cell events including division, differentiation, morphogenosis, fertilization, inflammation and metastasis. Although they are not formed by direct translation as in genomes and proteomes, they are important because many kinds of enzymes relating to their biosynthesis are under the control of genomes. Therefore, the carbohydrates in glycoconjugates are attractive as postscriptomes, and the method development for carbohydrate analysis is an urgent theme in glycobiology. Since a number of structurally resembling species of carbohdrates coexist in biological samples, their analysis requires the most efficient methods capable of high resolution and sensitive detection. For this reason capillary electrophoresis (CE) has become the most important tool for carbohydrate analysis. CE is, however, basically a method for ions, hence carbohydrates, which are generally neutral, are not good objects of CE. In addition, carbohydrates are normally difficult to sensitively detect, because they lack in chromophore/fluorophore. Chemical/enzymatic derivatization is the most appropriate strategy to solve these problems simultaneously. In this paper a number of methods for derivatization of carbohydrates for CE are compared and criticized, and the 1-phenyl-3-methyl-5-pyrazolone (PMP) method and the methylglycamine-4-nitro-2, 1, 3-benzodiazole tagging method (MG-NBD method) are selected as the most suitable methods for routine and ultramicro analyses of carbohydrates, respectively. A number of examples for their application are presented. A technique of automation of such analysis by CE with in-capillary derivatization is also presented. Miniaturization of the PMP method to microchip electrophoresis (ME) has realized rapid analysis of carbohydrates in few ten seconds. The versatile functions of carbohydrates stem from their binding with particular proteins, and therefore the study of carbohydrate-protein binding is also important. CE can be performed in free solution, not necessitating addition of any supporting materials. Owing to this single-phase property of CE one can observe interaction occurring in a capillary as the migration time change of either of these reactants in running buffer containing the counterpart. By mathematical treatment of such migration time change, we could develop a series of methods for micro-ultramicro estimation of association constant. On the other hand we could succeed in finding out a number of proteins in biological samples, which can specifically bind to glycans and glycoconjugates.