Cyclofructans (CFs) and their derivatives have recently been proven to be efficient chiral selectors (CSs) for the enantioseparation of several analytes in CE, HPLC, and GC. In this study, the chiral separation ability of a number of native and derivatized CFs was examined in CE. Particularly, six different CFs, with different derivatization groups and cavity sizes [native CF-6 and CF-7, isopropyl cyclofructan-6 (IPCF-6), IPCF-7, sulfated cyclofructan-6 (SCF-6), and SCF-7] were used as CSs for the enantioseparation of huperzine A, warfarin, and coumachlor. Almost all of the examined CFs, except from SCF-6 & -7, demonstrated relatively low and sometimes no chiral separation ability for huperzine A. In an effort to improve both resolution and efficiency, the chiral ionic liquid D-Alanine tert butyl ester lactate (D-AlaC(4)Lac) was added into the BGE. In most of the cases, the combination of CF with D-AlaC(4)Lac resulted in an improvement in peak efficiency and/or resolution. When CF-6 was utilized with D-AlaC(4)Lac, a resolution of 1.4 was obtained, while the use of IPCF-6/D-AlaC(4)Lac provided a baseline enantioseparation. Although the combination of SCF-7 and 40 mM D-AlaC(4)Lac did not affect resolution, it dramatically increased peak efficiency from 24 000 to 117 000. In the case of warfarin and coumachlor, IPCF-6 and IPCF-7 proved to be the most effective CSs. It is, therefore, concluded that the size of the cavity and the CF derivatization are the key parameters for the chiral separation capability. It is also clear from this study that D-AlaC(4)Lac is necessary for improved peak efficiencies and resolutions.