A type of chiral monolithic column was developed for the enantioseparation by capillary electrochromatography (CEC). Based on the high activity of epoxy group of glycidyl methacrylate monolith, the bovine serum albumin(BSA) bonded chiral stationary phase(CSP) was prepared by a direct derivatization process. The tested optimal separation conditions were the separation voltage of -5 kV, the UV detector wavelength of 214 nm, the sample injected time of 5 s and the phosphate buffer solution concentration of 10 mmol/L. Under the optimum conditions, the separation performance of the BSA-CSP capillary electrophoresis column for four amino acids and a chiral drug(warfarin) were studied. All of the resolution was above 1.90, and the best resolution was more than 8.81. The analysis time for each pair of enantiomers was less than 15 min.