An online preconcentration method based on electrostatic interaction between the analytes and inner surface of the capillary column was developed for the determination of zwitterionic analytes such as amino acids in CE coupled with a DAD. The amino acids possessed positive charges when they were dissolved in an acidic solvent. When they were injected into the column, they were attracted by the negatively charged inner surface of the fused-silica capillary column. An etched column was used to increase the area of the capillary's inner surface and, consequently increase the electrostatic interaction between the amino acids and the inner surface of the capillary column. It was found that when the sample was injected at 10 psi for 1 min and the pH value of the sample was 4, the amount of amino acids attracted to the inner surface of the capillary was maximum. Under these optimized experimental conditions, the detection sensitivity of CE-DAD was enhanced by 5200, 2800, and 3100 times for asparagine, tryptophan and phenylalanine, respectively, compared with normal CE separation. The method provided good reproducibility in terms of both migration time and peak height. It can be successfully used for the preconcentration zwitterion.