SummaryThe separation of enantiomers of rather simple molecules, such as alkanes and alkanoic acid esters substituted at the 2-position, has been investigated on alkylated 0-cyclodextrin stationary phases. By observing the effect of varying the substrate and the cyclodextrin alkylating agent it has been possible to propose a mechanism for the separation.The most important factors seem to be hydrophobic interactions and the ability of the cyclodextrin to change its conformation to accept the guest molecule.