Enantiomeric pairs of 11 dansyl derivatives of α-amino acids were used as analytes in electrokinetic chromatography to test the ability as chiral selectors of two pure derivatives of β-cyclodextrin: the ethylendiamine derivative in primary position (CDen) and a member of a new class of receptors, the cysteamine-bridged hemispherodextrin THCMH. The selectivity obtained by the presence of the hemispherodextrin, appears particularly promising as shown by the large values of resolution obtained. The importance of a detailed analysis of these data is discussed in terms of suggestions for a rational approach to separation science.