It has been suggested that peroxide could act as an enhancing agent for gold‐catalyzed oxidation reactions in the aqueous phase. Here, we probe the potential role of peroxide in the catalytic oxidation of glycerol on gold in the aqueous phase by electrochemical techniques and find that neither the presence of oxygen nor peroxide leads to a significant enhancement of the overall oxidation activity or product selectivity at low temperature. In alkaline media, there appears to be a small suppression of the formation of glyceraldehyde in the presence of hydrogen peroxide but there is no major influence on the overall oxidation pathway. In neutral and acidic media, glycerol oxidation on gold has low activity.