This catalyst is a new type of hydrogenation catalyst developed for hydrodesulfurization of coking crude benzene. It is mainly used for removing organic sulfur compounds such as mercaptan, thioether, disulfides and thiophene from coking benzene through hydrogenation reaction. Under the operating conditions of 2.4-3.0 MPa pressure, 280-370°C reaction temperature, liquid space velocity of 0.6-0.7 h-1 and hydrogen-oil ratio of 600:1-900:1, the thiophene content in the resulting oil can be reduced to ≤0.5 ppm, meeting the requirements of GB3405-2011 petroleum benzene standard. The catalyst features high desulfurization activity, low tribenzene loss, long service life and high stability.