The adhesion between glass or oxidized Si substrates and evaporated gold films in combination with an adherent intermediate layer of Ta, Si, Ge, or Cr has been investigated. The experimental results regarding changes of adhesion as a function of the relative thickness of the Au and underlayer films as well as time, environment, and treatment after deposition are described in detail. They can be explained in terms of the thermodynamic properties of the respective Au-underlayer systems: In the case of Au–Si and Au–Ge, alloying and diffusion processes play the dominant role while, for Au–Ta, oxidation of Ta is responsible for adhesion changes. Most importantly, in the Au–Cr system, none of the above processes are effective, at least up to 450 °C. Consequently, no loss of adhesion was observed for periods of one month and thicknesses of the Cr layer of only about 10 Å.