The reduction of chemisorbed iodine to iodide has been studied at smooth polycrystalline gold electrodes in aqueous electrolyte in order to examine the influence of adsorption on the iodine/iodide redox couple. It has been found that a single‐electron reduction, which results in the desorption of iodide ions from the surface, occurs at a potential approximately 900 mV negative of that at which the redox takes place in the dissolved state. This large negative shift indicates that, in the chemisorbed state, zero‐valent iodine is more stable than iodide by about 160 kJ/mol. The reductive desorption of surface iodine from gold was also found to be independent of pH, unlike that on platinum in which the cathodic removal of iodine is always accompanied by hydrogen chemisorption, which renders the overall reaction pH dependent; this difference is ascribed to the fact that dissociative chemisorption of hydrogen does not occur as readily on gold as it does on platinum.