Capillary electrophoresis is useful for the studies of biomolecular recognitions and the screening of libraries. Its applications reported in the literature include the separation of racemic biomolecules, the measurement of binding constants, the estimation of kinetic rate constants, the determination of stoichiometries, the examination of electrostatic interactions, the estimation of effective charges and molecular weights of proteins, the characterization of enzymatic activities, and library screening for drug candidates in solutions. This technique demands only small amounts of samples, involves no radiolabeled or fluorescently labeled materials and chemically immobilized ligands, and does not require changes in spectroscopic characteristics upon binding. This paper reviews the most recent applications of capillary electrophoresis and its use in the analysis of biomolecules.