Avidin-liposome complex is a specific chiral selector used to separate the enantiomers of D,L-tryptophan,D,L-phenylthiohydantoin -serine(D,L-PTH-Ser),D,L-phenylthiohydantoin-threonine(D,L-PTH-Thr) and R,S-pioglitazone hydrochloride in capillary electrochromatography(CEC).The avidin is immobilized on the phospholipids coated in the capillary.The liposome used for the phospholipid coating contains l,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-(Cap biotinyl)(sodium salt) (Biotinyl-cap-DPPE)(16:0) and different proportions of L-α-phosphatidylserine(PS) in Tris(hydroxymethyl) aminomethane (Tris) buffer at pH 7.4.A good resolution and reproducibility was obtained by coating the capillary with Biotinyl-cap-DPPE/PS (80:20,mol%) followed by immobilization of 1 mg/mL of avidin solution in N-(2-hydroxyethyl) piperazine-N'-(2-ethanesulfonic acid) (HEPES) buffer at pH 7.4.A comparative study of chiral separation efficiency with different capillary coating methods and preconditioning conditions was conducted.Finally,the electrochromatographic method was successfully used to separate enantiomers of pioglitazone hydrochloride.Therefore,coated CEC will be a promising tool for pharmaceutical enantiomers separation in new drug development.