We studied the early stages of Cu electro-deposition and -dissolution on Au(111) over a wide over-potential regime by using high speed atomic force microscopy (HS-AFM) with a high temporal resolution. The HS-AFM images revealed an instantaneous nucleation mechanism where epitaxial nuclei were created at a low cathode overpotential. Nuclei with straight edges were caused by the influence of the Au(111) lattice, whereas arched and uneven edges were associated with rapid structural fluctuations of Cu adatoms. For deposits formed at a high overpotential, many fine column-like deposits covered the whole surface plane and the number of Cu nuclei increased with the cathode overpotential. These features were related to the masstransportation. Furthermore, we observed small clusters, a few nm in size, which remained on the substrate after the rapid dissolution process. (C) 2019 Elsevier Ltd. All rights reserved.