NiMoP/MCM41-γAl2O3 (NiMoP/AMx) supported catalysts have been investigated as a modification of MCM41 by using the sol–gel alumina incorporation method. Different catalysts were synthesized varying the Si/Al molar ratio (5, 10, 25 and 50). The aqueous solution method was used to impregnate the metallic species (NiMoP) on the AMx supports. A surface area high mesoporous solid was synthesized by using an organic template method. The incorporation of sol–gel alumina did modified the hexagonal array of the mesoporous material MCM41 when the preparation of AMx supports was carried out. The XRD patterns of the catalytic supports show that phases, MCM-41 and γ-Al2O3 exist, indicating the presence of the two materials in the synthesized solids. Raman spectroscopy also indicates the formation of NiMoO4 and MoO3 which are more difficult to sulfide and produce MoS2 and Ni3S2 as separated sulfides instead of the NiMoS phase. The symmetries of the materials were determined through UV–vis where octahedral NiO as well as tetrahedral and octahedral Mo were found. The main reaction products were biphenyl (BP), cyclohexylbenzene (CHB) and bicyclohexyl (BCH) when the materials were tested in the HDS of DBT.