Highly sensitive and universal indirect chemiluminescence detection for capillary electrophoresis of cations was described. This novel method is based on use of the ultrasensitive cobalt(II) as a probe ion in the running buffer. A strong and stable background chemiluminescent signal can be generated by the luminol-hydrogen peroxide reaction catalyzed by cobalt(II) ion. Displacement of the cobalt(II) probe ion in the running buffer by a migrating sample cation results in a quantifiable decrease in the background signal. The conditions for electrophoresis and the chemiluminescent reaction were systematically investigated using a commercial capillary electrophoresis instrument with an in-house-built chemiluminescence detector. Under the optimal conditions, the detection limits of the concentration for manganese(II), cadmium(II), nickel(II), lead(II), and 14 lanthanides were (3.0-6.0) x 10(-9) mol/L (S/N = 3), which was approximately 3 orders of magnitude better than indirect UV detection and 2 orders better than indirect laser-induced fluorescent detection. A mixture of 18 metal ions including 14 lanthanides was efficiently separated within 3.5 min using lactate to partially complex the metal ions. Our data demonstrated that CE with indirect CL detection was a powerful and universal tool for analysis of inorganic and organic cations.