New single-isomer, cationic β-cyclodextrins, including mono-6-deoxy-6-pyrrolidine-β-cyclodextrin chloride (pyCDCl), mono-6-deoxy-6-(N-methyl-pyrrolidine)-β-cyclodextrin chloride (N-CH 3-pyCDCl), mono-6-deoxy-6-(N-(2-hydroxyethyl)-pyrrolidine)-β- cyclodextrin chloride (NEtOH-pyCDCl), mono-6-deoxy-6-(2-hydroxymethyl- pyrrolidine)-β-cyclodextrin chloride (2-MeOH-pyCDCl) were synthesized and used as chiral selectors in capillary electrophoresis for the enantioseparation of carboxylic and hydroxycarboxylic acids and dansyl amino acids. The unsubstituted pyCDCl exhibited the greatest resolving ability. Most analytes were resolved over a wide range of pH from 6.0 to 9.0 with this chiral selector. In general, increasing pH led to a decrease in resolution. The effective mobilities of all the analytes were found to decrease with increasing CD concentration. The optimal concentration for most carboxylic acids and dansyl amino acid was in the range 5-7.5mM and >15mM for hydroxycarboxylic acids. 1H NMR experiments provided direct evidence of inclusion in the CD cavity.