Enantiomer migration order (EMO) in chiral capillary electrophoresis (CE) represents a challenging issue, referred to in less than 20% of the articles on CE enantioseparations. This review article will (i) illustrate the actuality of the topic, (ii) discuss some technical problems related to EMO in CE enantioseparations, (iii) examine the principal differences between CE and other separation techniques from the viewpoint of enantiomer elution order, (iv) demonstrate the potential for a designed reversal of EMO in CE, and (v) emphasize the importance of studying EMO for better understanding of chiral CE as well as its more effective application. Along with CE, the results obtained by other instrumental techniques such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (IMS), X-ray crystallography, as well as molecular modeling calculations will be shortly discussed. Rather than referring to all published examples of the opposite migration order of enantiomers in CE, the emphasis will be on general aspects. Recently, the reversal of the EMO was described in detail in a book chapter (Chankvetadze, B., Capillary Electrophoresis in Chiral Analysis, Wiley & Sons, Chichester, UK 1997, Chapter 12) as well as in three review articles [1, 3, 4].