Electrogenerated chemiluminescence (ECL) of lucigenin is induced at oxide-coated aluminum electrodes in aqueous solution by cathodic pulse polarization. This ECL can be enhanced by the presence of coreactants such as peroxodisulfalte. The present method is based on the injection of hot electrons into the aqueous electrolyte solution, which probably results in the generation of hydrated electrons as reducing mediators. The successive one-electron redox reactions result in the excited states of lucigenin or its fragmentation products. The method can detect lucigenin over several orders of magnitude of concentration with detection limit below nanomolar concentration level. In addition, the relatively long lifetime of the ECL of lucigenin makes time-resolved detection possible. This study suggests that the derivatives of lucigenin can be utilized as electrochemiluminescent labels in aqueous solution in bioaffinity assays at thin insulating film-coated cathodes. The cathodic ECL reaction mechanisms are discussed. (c) 2006 Elsevier B.V. All rights reserved.