ZnSe/GaAs (001) heterovalent heteгostructures are fabricated by metalorganic vapor phase epitaxy. During the growth, both GaAs and ZnSe surfaces are kept atomically flat to achieve precise control of the interface formation. Interface composition, Ga/As, are controlled by means of either Zn or Se treatment of a GaAs surface, and then ZnSe growth follows. Consequently, it is revealed by X-ray photoemission spectroscopy (XPS) that artificial control of Ga/As from 1.0 to 2.8 leads to the variation of valence band offsets from 0.6 to 1.1 eV. Based on the electron counting model and layer-attenuation model, it is proposed that the As plane just below the interface consists of As, anti-site Ga and As vacancy.