The complex supporters with different mass fraction of TiO ₂ for preparation W ₂N/γ-Al ₂O ₃-TiO ₂ catalyst were made by titanic acid tetra-butyl ester sol-gel method and γ-Al ₂O ₃ as raw materials. The catalyst precursors, WO ₃/TiO ₂-Al ₂O ₃, with different WO ₃ content were prepared at 500 ℃ baking for 5 h after loading ammonium paratungstate。The precursors were deoxidized and nitrification in H ₂/N ₂ (volume ratio of 1∶(4~5) gas-flow of 10 800 h-1 through temperature programmed could get the catalysts. And the catalysts were characterized by means of XRD，BET，XPS and TG/DTA. The influence of mass fraction of TiO ₂ on its specific surface, its acid amount and its performance for thiophen HDS was investigated in miniature high pressure device of the fixed bed. The results show that when the mass fraction of TiO ₂ is 6% in the catalyst, its acid amount and its specific surface are the largest, they are 0.184 9 mmol/g and 107.2 m ²/g respectively. And the activity of the catalyst for thiophene HDS is the best, at 330 ℃, pressure 3 MPa, weight hour space velocity 6 h-1, hydrogen oil ratio 900∶1, the conversion rate of thiophen is up to 56.4%. 