Cyclofructans (CFs) are a class of cyclic oligosaccharides with a crown ether skeleton. No enantioseparations have previously been reported using this class of chiral oligosaccharides in chromatography or electrophoresis. CFs and their sulfated derivatives were examined as chiral selectors using CE. The native CFs showed no enantioselectivity toward any tested compounds, while the sulfated CFs showed exceptional selectivity toward many cationic analytes, including primary, secondary, and tertiary amines and amino acids. Enantiomeric resolution factors as high as 15.4 were achieved within short analysis times (generally below 10 min). The effect of buffer type, buffer concentration, buffer pH, chiral selector concentration and organic modifier concentration was examined and optimized.