Two surface superstructures (4×1)-O and (2×2)-S, induced respectively by oxygen and sulphur segregation on the V(001) surface, are studied in detail by ARVPS. The energy levels and symmetry of the adsorbate surface states derived from S- and O-ordered adsorbate over-layers are determined. Experimental evidence shows that the adsorption sites of oxygen on V(001) surface are four-fold hollow sites. All the experimental results consist with theoretical calculations, and are similar to that for oxygen on Ni(001) and Cr(001) surfaces.