Enantiomer separations by capillary electrophoresis (CE), using proteins as chiral selectors-affinity capillary electrophoresis (ACE) with free solutions and capillary electrochromatography (CEC)-with protein immobilized capillaries, are reviewed. The separation principle, recent advances in this field and some interesting topics are presented. In ACE, various enantiomer separations have been already reported using either plasma proteins or egg white ones. Miscellaneous proteins were also explored in the last few pears. On the contrary, only a limited number of enantiomer separations have been successfully achieved in CEC. CEC is not yet mature enough to date, and further investigations, such as efficiency, durability and reproducibility of capillaries, will be necessary for the use of routine analyses. The study of enantioselective drug-protein binding is important in pharmaceutical developments. Some applications including high-porformancee CE/frontal analysis (HPCE/FA) are introduced in this paper. (C) 2001 Elsevier Science B.V. All rights reserved.