In this work, the capillary gas chromatographic enantiomer separation of eight congeneric compounds with general formulae CH3-HCX-COOC2H5 (where X = Cl, Br, I, CN, OH, OC2H5, OC6H5 and NHCOCF3) on four different permethyl- and 2,6-di-O-methyl-3-O-pentyl- beta- and gamma-CD stationary phases has been studied. The separation of enantiomers was evaluated in terms of the interactions of the X substituent of studied derivatives, as well as the nature of the 3-O-alkyl group in the 2,6-di-O-methyl-3-O-alkyl-CDs and the CDs cavity size. The differences in thermodynamic data [deltaH and -deltaS] obtained for studied compounds and the selectivity of modified beta- and gamma-cyclodextrin phases in gas chromatographic separation were evaluated. deltaH values were compared with a deltaH value of an achiral standard (ethyl propionate, where X = H) in order to obtain the contribution of a particular substituent to the overall interaction energy. It was shown that the variation in the enantiomeric separation with temperature and the retention order of these compounds on a given cyclodextrin capillary column depends on the nature of the substituents bonded to stereogenic carbon atom. It was found that the temperature dependencies of selectivity factors, In a on 1/T, were both linear as well as non-linear, inter alia depending on the number of glucopyranose units of the CD derivatives. The enantiospecific thermodynamic data [delta21(deltaH)] and [-delta21(deltaS)] which characterize the chiral recognition in the separation system were used to gain more insight into the mechanistic aspects of the enantioseparations on permethylated and 2,6-di-O-methyl-3-O-pentyl-beta- and gamma-cyclodextrins.