Highly sensitive chemiluminescence detection for capillary ion analysis has been developed, The new idea lies in using the chemiluminescence reagent luminol as a component of the separation electrolyte, thus preventing loss of the light signal where luminol and H2O2 are mixed in advance in conventional now injection analysis or ion chromatography chemiluminescence detection, Signal enhancement is achieved by sample stacking injection in the electrophoresis process, The detection limit (S/N = 3) of 20 zmol (5 x 10(-13) mol/L) for cobalt(II) is similar to 2 orders of magnitude better than the most sensitive results (1.7 x 10(-11) mol/L) reported so far, Detection limits are 2 amol, 80 amol, 740 amol, and 100 fmol for copper(II), nickel(II), iron(III), and manganese(II), respectively, The sensitivity is significantly better than that in the electrochemical detection and the commonly used UV detection in capillary ion analysis. The capillary electrophoresis-chemiluminescence detector has been used to separate five metal ions, cobalt(II), copper(II), nickel(II), iron(III), and manganese(II), within 8 min with an average theoretical plate number of 4.6 x 10(5).