The effect of ionic hydrodynamic radius in the separation of capillary zone electrophoresis is discussed by using maltooligosaccharide as model compounds. The linear correlation between mu(cp) and n(-1) (n is the number containing the glycosyl units) has been derived and has experimentally been verified with various buffer systems and separation voltages. The results show that hydrodynamic radius is one of the actual factors in HPCZE other than molecular weights. The proposed equation could provide the approach determining glycosyl units of maltooligosaccharide.