The change in the chemical surface state of a V-4Cr-4Ti alloy after heat treatments in vacuum at temperatures from 573 to 1273 K was investigated by means of X-ray photoelectron spectroscopy. Before heating, the surface of the as-polished alloy was covered with a V oxide film. Diffusion of oxygen into the bulk started at around 673 K, and the alloy surface gradually became metallic. Oxygen, however, did not disappear from the surface completely. Surface segregation of Ti was observed as the temperature increased. The concentration of Ti reached 20 at% at 1273 K. No significant segregation of Cr or other impurities were observed. This surface segregation of Ti significantly reduced the surface reaction rates of H 2 and D 2 . The isotope effect on the surface reaction rates of H 2 and D 2 was not observed under the present experimental conditions.