The properties of the confined aqueous layer potentiodynamically formed on polycrystalline gold in aqueous phosphate and sodium dodecylsulphate solutions were studied using voltammetry, ellipsometry, and contact angle measurements. The nature of the incipient oxide layer was analyzed as a function of the cycling time in the double layer-oxide monolayer potential region. The replacement of the electrolyte by hexane allows the increase of the optical signal. Different potential cycling conditions change the homogeneity of the confined aqueous incipient oxide layer leading to different structural characteristics.