Abstract: A method of pressurized capillary electrochromatography was proposed for the resolution of enantiomers of mexiletine using hydroxypropyl-β-cyclodextrin (16 g·L-1) as selective chiral agent.A mixed solution of acetonitrile and 10 mmol·L-1 phosphate buffer solution(1+1 by vol.) of pH 2.5 was used as mobile phase.The separation voltage of 10 kV and temperature of capillary column of 20 ℃ were chosen.Under the optimized conditions,the enantiomer of mexiletine was successfully separated within 4 min with resolution factor of 1.51.