Polycrystalline copper films thicker than 100 nm were evaporated on silicon wafers with their native oxide under ultrahigh vacuum conditions leading to an rms roughness of ~2 nm of the copper film. X-ray photoelectron spectroscopy (XPS) revealed a clean copper surface with only traces of oxygen. The samples were exposed to air, leading to an oxide film consisting of CuO. TiO films were subsequently deposited onto the oxidized copper films from a resistively heated tungsten boat with the substrate at room temperature. The TiO films exhibited good adherence and were amorphous. XPS measurements revealed that the TiO films were contamination-free and that the first layers of TiO reduced the thin native oxide of the copper substrate from Cu(II) into Cu(I) or Cu(0) and transformed the TiO into TiO2 at the interface.