Reversal of enantiomer migration order (EMO) is summarized in chiral c
apillary electrophoretic systems. Different examples of this phenomeno
n are classified and in some cases the mechanisms of reversal of EMO a
re discussed. Enantiomer elution order in pressure-driven separation s
ystems depends only on the binding interactions between a solute and a
chiral selector. In contrast to this, EMO in electrokinetically-drive
n separation systems, besides the solute/selector association, also de
pends on the mobilities of electroosmotic flow (EOF), the chiral analy
te and the chiral selector. The reversal of EMO in capillary electroph
oresis (CE), in contrast to chromatographic techniques, does not alway
s require the reversal of chiral recognition ability. Some new possibi
lities of a reversal of enantiomer migration order in CE are also desc
ribed from the authors' most recent research.