We have determined the surface structure of O/Cu(104) using X-ray diffraction. This surface was prepared by dosing Cu(115) with oxygen, transforming the clean surface into facets with {104} and {113} orientations. This method of preparation, in essence, naturally grows the (104)-oriented substrate concurrent with the O-covered surface, resulting in O/Cu(104) facets which are smooth and highly ordered. Our results indicate that the top three atomic rows significantly expand away from the bulk, but no Cu rows are missing. The Cu–O structures of this surface are similar to those present on other O on Cu surface reconstructions, but the adsorbed O inhabits two adsorption sites with notably distinct geometries. The relationship between the O/Cu(104) and O/Cu(001)[Formula: see text] structures, in particular, is discussed.