The electrochemiluminescence (ECL) behavior of luminol in oxygen-saturated dimethyl suffoxide (DMSO) solution at a polycrystalline gold electrode was studied under conventional cyclic voltammetric (CV) conditions. Corresponding to the reduction processes of oxygen, one ECL peak (ECL-1 at -1.40V versus SCE) with two shoulders (S1-1 at -0.55 V and S1-2 at -0.90 V) was observed on the curve of ECL intensity versus potential. Corresponding to the subsequent oxidation processes of oxygen-containing species generated by the reduction of oxygen, one ECL peak (ECL-2 at -0.34 V) with a shoulder (S-2 at -0.67 V) was found. Among them, ECL-2 was strongest; it was 10 times stronger than ECL in pH 13.0 aqueous alkaline solution under the same conditions. These ECL peaks and shoulders were found to depend on the presence of N-2 and O-2, potential scan range, water concentration, supporting electrolyte, and the concentration of luminol. The emitter of both ECL peaks was identified as 3-aminophthalate (Ap(2-)) by analyzing the ECL spectra. The origin for these ECL peaks is proposed to be related to the reactions of luminol with various oxygen-containing species such as O-2(center dot-), H2O2, OH- and O-2 electrogenerated by the redox reactions of dissolved oxygen at different potentials. The results indicate that the ECL of luminol was correlated to the redox behavior of oxygen in DMSO. The present work reveals that the solvent plays an important role in the ECL behavior of luminol. (c) 2006 Elsevier Ltd. All rights reserved.