Enantiomeric separations of some esters were studied by means of capillary gas chromatography using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl) cyclomaltoheptaose (or BSiMe) and heptakis(2,3-di-O-acetyl-6-O-tert-butyldimethylsilyl)cyclomaltoheptaose (or BSiAc) as stationary phases. The influence of analyte structure, e.g. the type and position of substituent together with ester chain length, on retention and enantioselectivity was systematically investigated. Thermodynamic data were also calculated in order to clarify the strength of analyte-stationary phase interaction and enantioselectivity towards these selected groups of esters. All esters with different substitution patterns were successfully separated with either BSiMe or BSiAc, or otherwise both of them. Generally, BSiAc phase exhibited greater enantioselectivity towards most analytes than BSiMe phase. From chromatographic and thermodynamic data obtained, it can be concluded that the structure of ester analytes plays an important role on separation. In most cases, the interaction of these two phases towards esters slightly increased with lengthening alkyl chain while enantioselectivity significantly decreased. Also, changing the position of substituent or chiral center caused changes in the interaction and enantioselectivity. Moreover, the degrees of interaction strength and sites as well as enantioselectivity of these esters depended upon the size and polarity of substituents.