On addition of trace amounts of luminol or lucigenin to the milligram amounts of barium peroxide (BaO 2 ) solid powder, strong chemiluminescent phenomena have been observed. Based on this observation, a novel on-line solid-phase chemiluminescence detector was designed for capillary electrophoresis. A 27 cm×75-μm I.D. column with a 0.3-cm length detection window was used. A small amount of BaO 2 powder was packed into the detection window section. After the separation of luminol, lucigenin and N-(4-aminobutyl)-N-ethylisoluminol (ABEI), the analytes may be detected on-line. The optimum conditions for the capillary electrophoresis separation and detection were investigated. The detection limits were 5×10 −8 , 7×10 −8 and 1×10 −8 mol/l for lucigenin, ABEI and luminol, respectively. The proposed method was also used for the separation and detection of two amino acids labeled with ABEI.