This paper reviews thermodynamic, spectroscopic and X-ray diffraction studies of SO42-, Cl-, Br- and I- adsorption at the Au(111) electrode surface. The thermodynamic experiments provided information about surface concentrations of specifically adsorbed anions, Gibbs energies of adsorption and the numbers of unit charge flowing to the interface per one adsorbed anion. Second harmonic generation and surface X-ray scattering revealed the affect of ionic adsorption on the electronic and crystallographic structure of the interface. The atomistic information derived from these microscopic studies was used to discuss the thermodynamic data and to verify the theoretical models of the interface. It has been shown that complete description of ionic adsorption at metal electrodes requires a concerted use of the macroscopic and microscopic techniques.