Poly(amidoamine)(PAMAM) dendrimer has a large number of terminal groups which can be functionalized by different kinds of ligands.A novel open-tubular CEC(OT-CEC) column in which BSA was bonded to inner wall of capillary as stationary phase through different generations of PAMAM dendrimer was developed.The obtained columns were characterized via labelling BSA with fluorescein isothiocyanate(FITC).Under the optimized condition,the resolution of D,L-Trp was gradually improved with the increase of PAMAM generation.By OT-CEC column modified with BSA-G3.0-PAMAM,the baseline separation of D,L-Trp can be obtained.