The voltammetric behavior of polycrystalline gold electrodes in 0.1 M sulfuric acid and the influence of prolonged repetitions of oxidation and reduction cycles at different scan rates on the surface morphology was studied. Slow (0.1 V s−1) as well as fast (1.0 V s−1) scan rates lead to an intense roughening of the electrode surface and the formation of a variety of different crystalline particles on it. These crystallites, their formation, and the influence of surface pretreatment were investigated with electrochemical methods, X‐ray diffraction measurements, and scanning electron microscopy. Additionally, an interpretation of the changing electrochemical signals of polycrystalline gold during prolonged potential cycling is given.