A novel capillary posess short-chain tertiary amine groups was successfully prepared. The cationic bonded-phase is effective in preventing the adsorption of positively charged proteins. Fast and high-resolution separations of basic proteins in ppm range with average efficiencies of 10300 plates/m were achieved also have a good reproducibility. In addition, the protonation ratio of bonded-phase and proteins will be changed by the pH of running buffer. Thus the influence of pH were experimentally investigated in this study.