The intrinsic support effect was explored in the preparation of NiW hydrodesulfurization catalysts through building correlations of catalytic performance to extensive surface characterization results. We found that the catalytic activity on the hydrodesulfurization of 3,methyl-thiophene correlates well with the normalized intensities data of NO adsorbed on Ni active sites. Also, a correlation between the catalytic activity and the number of tungsten edge atoms in the WS2 slabs was observed. The characterization of the NiW catalysts revealed that is possible to modulate the metal-support interaction by substituting the carrier. This specific interaction with each support derived into particular morphological parameters for the sulfide active phase. Optimal values for the slab length and the stacking of the WS2 slabs were proposed. (C) 2017 Elsevier B.V. All rights reserved.