Hydrotreating Ni heteropolytungstate catalysts have been prepared by impregnation of gamma-Al2O3 alumina with solutions of H3PW12O40 acid and its Ni salt. The nickel content is varied by adding Ni(NO3)(2) salt. The calcined samples are characterized by BET, IR, TPR, and XPS techniques. The catalytic activity is tested for HDS of thiophene. It is shown that the initial heteropolyanion, its lacunary analog, and nickel substituted heteropolyanion are present on the surface as a result of the interaction between the active component and the alumina support. The mixed NiWS phase formed after sulfidation determines the HDS activity of the catalysts.