Capillary electrophoresis (CE) recently has been shown to be a promisi
ng technique for the separation of optically active substances. This a
rticle describes the influence of the chiral selector on enantioselect
ivity. The author presents four classes of chiral selectors used as ps
eudostationary phases for direct enantioseparation using CE - host - g
uest complexation, micellar solubilization, ligand-exchange complexati
on, and polymer-based discrimination - and discusses their chiral reco
gnition mechanisms. He also addresses possible future developments in
this field.