Electrochemical measurements were carried out simultaneously with acquisition of in situ STM images of copper electrodeposition at low cathodic overpotentials and subsequent dissolution from the underlying polycrystalline gold surfaces. The morphologies of the copper deposits were examined for correlation with features of the current-voltage diagram. Copper growth is by nucleation and formation of 3D islands. During the initial stages of bulk copper growth the potentials were fixed at selected values and a balance observed between formation of polycrystalline copper nuclei and of copper crystals. After the first cycle of copper deposition and dissolution the morphology of the polycrystalline gold surface had apparently changed into a recrystallized phase of a copper-gold alloy. At a given stage of the cycle the potential of the electrode was found to depend linearly on the tip potential. In a wide range of tip potentials the onset of copper deposition and end of dissolution showed a potential separation of 59 +/- 5 mV indicating a single electron process.