A novel, eco-friendly, and stable homogeneous luminescent system for capillary zone electrophoresis (CE) detection was established, based on the chemiluminescence (CL) flash caused by mixing ferrate(VI) with luminol solution. It was found that the stable ferrate(VI) could be freshly electrogenerated in low-concentration NaOH solution for direct analytical application. To test this CL system, 8-hydroxyquinoline (HQ) was chosen as a model sample by CE detection.