The transformation of ethanol to its carbonyl compounds, namely acetaldehyde, ethyl acetate, acetic acid, and ketene, occurs on Au(111) with O-containing Au nanoparticles formed as a result of Au atom release upon ozone exposure. The product distribution strongly depends on the surface oxygen coverage. Ethoxy and acetate are identified as two key reaction intermediates during the oxidation of ethanol. The formation of acetaldehyde is due to the deprotonation of ethoxy, which can be further oxidized into acetate. The low-temperature formation of the ester, ethyl acetate, proceeds via the coupling of acetaldehyde with excess surface ethoxy. These reaction pathways appear relevant to heterogeneous processes catalyzed by supported gold nanoparticles, thus providing further insight into the mechanistic origin of gold-mediated oxidation of alcohols.