Abstract We deposited discontinuous gold films of various thicknesses onto muscovite mica by high vacuum evaporation. The deposition onto the substrate took place at room temperature, which is insufficient for epitaxial orientation of the metal. X-ray diffraction showed the absence of a defined azimuthal orientation of the polycrystalline gold film. Using the Au/mica system described as a substrate, a deposit of NH 4I from its saturated aqueous solution showed epitaxial orientation. When silver was evaporated onto the Au/mica system as a substrate (which was heated to 200 °C during the deposition), it showed epitaxial orientation as observed in a Laue photograph. This orientation was similar to the epitaxy of silver on a mica substrate. The Au/mica system keeps its epitaxial power for periods from 1 to 2 months. Substrates of mica without gold lose their epitaxial power in a few hours. The results obtained suggest that the discontinuities of the gold film make it possible for the same distribution of charges to exist on the metal surface as on the surface of the recently cleaved mica.