Ni-Mo-P/Al2O3-ZrO2 catalysts were prepared by temperature-programmed reduction in a H2 flow. The supports and catalysts were characterized by XRD and IR. Hydrodesulfurization of thiophene and hydrodenitrogenation of pyridine catalyzed by Ni-Mo-P/Al2O3-ZrO2 catalysts was carried out in a high pressure fixed bed reactor. The experimental results showed that the introduction of small amounts of ZrO2 on the surface of Al2O3 would reduce the strong interaction of P with Al2O3, and therefore, inhibited the formation of AlPO4. And the catalytic activity of thiophene hydrodesulfurization and pyridine hydrodenitrogenation over the catalyst has been improved with the adding of appropriate amount of Mo.