The mechanism of silver deposition on electrodes representing a cubic plane of silver single crystal with known surface topography was investigated. The exchange current densities on dislocation‐free intact planes and on stepped planes with exactly known step density were obtained by impedance measurements at high frequencies. It has been found that the exchange current density of the charge transfer reaction is about three orders of magnitude higher than the exchange current density of the reaction The comparison between experimental and calculated values of both the rate of propagation of monolayers and the slope of current‐square overvoltage relation has shown that the direct transfer mechanism plays a predominant role in metal deposition. The contribution of surface diffusion is negligible.