Alumina support with a high surface area was used to prepare alumina-supported MoP catalysts, varying the Mo and P loadings from 4% wt. to 53\%wt. Mo and P were loaded with an atomic ratio of Mo:P=1. The presence of different phosphate species was detected on all catalysts by NMR and electron diffraction techniques. The AlPO₄ phase was identified for highly loaded MoP catalysts (> 26 wt% of theoretical MoP). The catalytic materials were tested in hydrodesulfurization (HDS) of Dibenzothiophene (DBT) under high temperature (593 K )and pressure (5.5 MPa ) conditions and the highest activity for HDS of DBT was obtained with the catalyst containing Mo 9.9 wt% (13% wt of theoretical MoP) keeping an atomic ratio P/Mo=1. A structural model is proposed considering the Mo and P loading. The catalyst with the best activity showed high surface area (>200 m²/g).