A facile, sensitive, and selective method was developed for the simultaneous separation and determination of copper(I) [Cu+] and copper(II) [Cu2+] ions using CE with direct UV detection. The copper ions were complexed with a 1.5 mM bicinchoninic acid disodium salt solution at pH 8.7 prior to analysis. Acetate buffer (2 mM) was used as the CE running buffer. Parameters affecting CE separation such as sample pH, applied voltage, concentration of complexing agent, nature of the buffer solution, and interferences by other metal ions, were evaluated. The LODs for Cu+ and Cu2+ were 3.0 and 2.5 mu g/mL (S/N = 3), respectively. The developed method allows the simultaneous determination of Cu+ and Cu2+ in less than 5 min with RSDs of between 5.3 and 9.5% for migration time and between 3.4 and 9.7% for peak areas, respectively. At optimum conditions, the percentage recoveries of Cu+ and Cu2+ were found to be 99.4 and 99.5%.