The two‐ and three‐dimensional nucleation and the metal ion adsorption process are discussed as initial steps for electrocrystallization on the same or on a foreign substrate. The metal ion adsorption takes place in the underpotential range, which is more positive than the equilibrium potential of the nucleated metal/metal ion electrode. Thermodynamic considerations show that an overlapping of disturbing processes in the underpotential range can be characterized by a factor , which is called charge‐coverage coefficient or electrosorption valency. It is a function of different independent variables. The metal monolayer model is satisfied only in the simplest case for (valency of metal ions in solution).