The deactivation of the Ni2P/SiO2 catalyst in the hydrodechlorination of chlorobenzene was studied. To better illuminate the reasons for the deactivation, the effect of HCl on the structure and activity of Ni2P/SiO2 was investigated. For comparison, the deactivation of the Ni/SiO2 catalyst was also involved. It was found that the Ni2P particles possessed good resistance to HCl poison and to sintering, which is ascribed to the electron-deficiency of Niδ+(0<δ<1) site in Ni2P. Acted as the Lewis and Brönsted acid site, the Niδ+ site and the POH group on Ni2P/SiO2 catalyzed the formation of the carbonaceous deposit that was difficultly eliminated by hydrogenation. The carbonaceous deposit covered the active sites and might also induce a decrease in the Ni2P crystallinity, subsequently leading to the Ni2P/SiO2 deactivation. Different from Ni2P/SiO2, Ni/SiO2 was mainly deactivated by the chlorine poison and the sintering of nickel crystallites.