Perphenylcarbamoylated beta-cyclodextrin bonded-silica particles (5 mu m) were packed into 75-mu m fused-silica capillaries, and used for the enantiomer separation of neutral and basic solutes by pressure-assisted capillary electrochromatography. Triethylammonium acetate and phosphate buffer were employed as the BGEs. A cathodic EOF was observed with these two BGEs. Seven chiral analytes were successfully resolved into their enantiomers under optimized conditions, and five of them could be baseline-separated within 12 min due to their high electrophoretic mobility. Better results were achieved with phosphate buffer as the BGE. The effects of organic content and pH on the enantioseparation were also investigated.