Unsupported Ni-Mo-W sulphide hydrodesulphurization (HDS) catalysts were prepared by ex-situ decomposition of trimetallic Ni-Mo-W precursors varying the nickel concentration. Firstly, the trimetallic precursors were treated in a stainless steel vessel of 45mL volume at 523K for 2h under argon atmosphere. Subsequently, the respective thiosalt was decomposed under a reductive atmosphere of H2S/H2 (15vol.% H2S) from room temperature to 673K. A series of four catalysts was tested in HDS of dibenzothiophene (DBT). The catalysts were labeled as Ni0.5, Ni1 and Ni2 according with the molar ratio of Ni in the sample. In addition, a precursor with a molar ratio Ni-Mo-W of 2:1:2 was prepared varying the concentration of tungsten, named as W2. The catalysts were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and BET specific surface area measurements.The ex-situ activation method leads to catalysts with a distribution of specific surface areas from 8 to 34m2/g, showing type IV adsorption–desorption isotherms of nitrogen typical for mesoporous materials, and poorly crystalline structures with different morphology, and varying phase composition. The Ni:Mo:W atomic ratios for the trimetallic catalysts show variations and are slightly smaller than those expected. The sample labeled as Ni-Mo-W2 showed the highest catalytic activity in the HDS of DBT (k=12×10−7mol/gs).