Enantiomers of nine arylglycine amides synthesized were successfully separated by capillary electrophoresis (CE) using highly sulfated beta-cyclodextrin (HS-beta-CD) as a chiral selector. Baseline enantioseparation of the analytes was obtained within 6 min at neutral pH but not the commonly used acidic condition. HS-beta-CD content, buffer type and concentration, and non-chiral additive were studied and optimized for high resolution and fast speed. A reproducible running buffer system composed of 15 g/L HS-beta-CD, 0 or 10% (volume fraction) methanol and 20 mmol/L 3-(N-morpholino) propane sulfonic acid at pH 6.5 was obtained. The D-enantiomer always migrated ahead of the L-enantiomer for all the 9 pairs of arylglycine amides. The migration order was found to be dependent on the structure of the solutes.