Six different cyclodextrins with varying cavity size and rim substitution were used as chiral agents for the enantiomeric separation of eight chromane compounds or analogues using capillary electrophoresis. It is shown that the cyclodextrin type and concentration have a large influence on the enantiomeric separation obtained for these compounds. A chiral resolution of 1.4 or better could be obtained for all the substances with either substituted heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin or unsubstituted γ-cyclodextrin as the chiral selector. The influence of the γ-cyclodextrin concentration, ionic strength and pH on the chiral separations was also investigated with a multivariate screening design. The detection limit and resolution of the present method allow determinations of the investigated compounds down to a chiral impurity of less than 0.1 % (area/area).