The application of the principle of ligand-exchange capillary electrophoresis to two substance classes is described. As chiral selector N-(2-hydroxyoctyl)-L-4-hydroxyproline-copper(II) complex was used. This principle was applied to the chiral separation of alpha-hydroxy acids and drugs containing amino alcohol structure such as beta-blockers. The enantioselectivity was found to be strongly dependent on pH corresponding to the optimal conditions for complex formation for each structure class.