Small atomic gold clusters in solution, Au n , stabilized by tetrabutyl ammonium bromide (TBABr), have been synthesized by a simple electrochemical technique, based on the anodic dissolution of a gold electrode in the presence of TBABr salt, and using acetronitrile as solvent. The presence of clusters in the range Au3-Au11 were detected by MALDI-TOF spectroscopy, and further characterized by UV-vis absorption spectroscopy, TEM, AFM, X-ray diffraction, and cyclic voltammetry. Clusters display a semiconductor behavior with a band edge of approximately 2.5 eV. We report here their extraordinarily high electrocatalytic activity toward the O2 reduction reaction in acid solutions, which can explain Zhang's results, showing that a four-electron mechanism seems to occur because of the facile reduction of H2O2 on gold clusters compared to bulk gold or larger gold nanoparticles.