Titania-supported 12-molybdophosphoric acid and its Co(Ni) salts were studied by X-ray photoelectron spectroscopy and Fourier transform IR spectroscopy in the mid-infrared range and of adsorbed nitric oxide and pyridine. Hydrodesulphurization of thiophene was used as test reaction of the samples. The results provide additional support for the preservation of phosphoro-molybdate anion on titania-support after its supporting. The highest activity of nickel promoted catalysts may be caused by an increase in dispersion of molybdenum and its lighter reduction.