A concomitant chemiluminescence burst can be detected when hydrogen peroxide is injected into the solution containing either free or chelated ferrous iron. The duration of the burst is slightly longer than the time for the oxidation of Fe2+. The luminescence intensity is a quadratic function of the initial concentration of H2O2 and is dependent on Fe2+ concentration. The scavengers of hydroxyl radical effectively inhibit, while the previously added ferric ions enhance, the luminescence. It is proposed that the excited species responsible for the luminescence is created by the reaction of hydroxyl radical with ferric iron. The theoretical analysis based on such a mechanism can fairly well interpret the experimental observation. The present study suggests that an excited ferryl species may be formed in Fenton reaction.