The second member of the single-isomer, sulfated gamma-cyclodextrin family, the sodium salt of octa(6-O-sulfo)-gamma-cyclodextrin (OS) has been synthesized, characterized and used to separate the enantiomers of nonelectrolyte, acidic, basic, and ampholytic analytes by capillary electrophoresis in acidic aqueous background electrolytes. The anionic effective mobilities of the nonelectrolyte and anionic analytes increased with increasing concentration of OS. The effective mobilities of strongly complexing cationic analytes became anionic with very low OS concentrations and passed local anionic effective mobility maxima as the OS concentration, and along with it, the ionic strength, of the background electrolyte increased. The effective mobilities of the weakly binding cationic analytes became only slightly anionic at high OS concentration values and did not show the local anionic effective mobility maxima. For nonelectrolyte analytes, separation selectivities decreased with increasing OS concentration. For cationic analytes, separation selectivities were highest where the effective mobilities of the less mobile enantiomers approached zero. OS proved to be a broadly applicable chiral resolving agent.