Abstract: Because of the similarity of chemical properties between sulfur and oxygen, the formation of c(2×2)-S superstructure on the surface of NiW substrates is effective to control the texture of the epitaxial oxide buffer layers on the surface of metal Ni substrates. A new technological route was put forward to form the c(2×2)-S superstructure on the surface of substrates by the sublimation (at 120°C), adsorption and desorption of elementary sulfur. The X-ray photoelectron spectra (XPS) analysis indicated that notable amount of S element can be observed on the metal substrates treated by the new method. The ratio of Ni atoms to S atoms is in accord with the coverage of c(2×2) structure which is 0.5. The results of the buffer layer prepared on the surface with c(2×2)-S superstructure showed that the new sulfuration method improves the physical and chemical properties of the surface of NiW substrates and is propitious for the growth of epitaxial oxide layers.