Metal‐oxide/metal interfaces play an important role, for example, in the joining of an oxide ceramic to a metal for sealing applications. In order to probe the chemical and physical properties of such an interface, we have performed Auger electron spectroscopic(AES) and temperature programed desorption(TPD) experiments on a model system composed of very thin films of Cr, Fe, Ni, or Cu evaporated onto a very thin thermally grown oxide on a W single crystal. Monolayerfilms of Fe and Cr were found (by AES) to completely wet the oxide surface upon deposition, and were stable up to temperatures at which the films desorbed (≊1300 K). In contrast, monolayerNi and Cufilms formed three‐dimensional islands exposing the oxidized W surface either upon annealing (Ni) or even upon room‐temperature deposition (Cu). The relative interfacial interaction between the overlayer metal and the oxide, as assessed by TPD, increases in the series Cu<Ni<Fe<Cr. This trend follows the heats of formation of the various oxides of these metals.