Enantiomeric separation of some basic compounds, namely selegiline, amphetamine, and clenbuterol, was studied by capillary electrophoresis using an uncharged -cyclodextrin polymer added to the background electrolyte at pH 2.5. Both complexation and resolution were influenced by the concentration of the chiral polymer confirming our previous results obtained in our earlier work for a wide number of pharmaceutical compounds. In this further study, we examined the influence of different organic additives to the background electrolyte on the enantioselectivity of the chiral selector, also using an extended number of analytes. In most cases, the use of an organic additive resulted in a decrease of resolution. However opposite to that, in some cases, e.g. ephedrine, the organic solvent proved to be essential to achieve enantiomeric resolution. Furthermore the influence of the capillary temperature on the resolution of the analytes was evaluated. Increase of temperature had a deleterious effect on the resolution of the enantiomers. For ephedrine, however, relatively high temperature (50 °C) proved to be advantageous, for the resolution of the optical isomers.