In this paper, Ca-Ni 2 P/SBA-15/Cord monolithic catalysts, with various contents of Ca, the different loading of Ni 2 P and molar ratio of P/Ni, and cordierite honeycomb ceramic (Cord) as the support, were prepared. The effect of Ca on the structure of Ca-Ni 2 P/SBA-15/Cord monolithic catalysts and catalytic performance for hydrodesulfurization (HDS) of the dibenzothiophene (DBT) were investigated. X-ray diffraction and N 2 adsorption–desorption was used to characterize the structure of monoliythic catalysts. The results showed with the increase of Ni 2 P, the surface area of monolithic catalysts decreased from 179.5 to 174.8m 2 /g, and the diameter distribution of monolithic catalysts decreased 6.12 to 5.51nm. Pure Ni 2 P was formed when P/Ni=0.8 among the molar ratio of P/Ni from 0.5 to 1.5. Other ratios showed the mixture of Ni 2 P and Ni 12 P 5 . The DBT conversion over Ca-Ni 2 P/SBA-15/Cord monolithic catalysts could reach more than 99% at 380°C, and the main product was CHB by the mechanism of hydrogenation route. Suitable contents of Ca could improve the surface area of the sample and enhance the conversion of DBT. But the extra contents of Ca could also adsorb H 2 S and restrain the conversion of DBT.