Unsupported A-Mo-W (A = Ni or Co) sulphide catalysts were obtained from mixed oxides containing different W:Mo ratios. An in situ liquid-phase sulphidation of the mixed oxides in a batch reactor was followed by catalytic tests in a liquid-phase reaction (at 613 K and 70 bar), using a mixture of dibenzotiophene (DBT) and tetralin (THN) as the feed. After the catalytic tests, the bulk sulphide catalysts were characterised by nitrogen physical adsorption, XANES/EXAFS, SEM and HR-(S)TEM. The HR-TEM images showed randomly oriented, stacked-layer particles typical of Mo (W) sulphides and an elemental HR-STEM mapping evidenced Mo/W homogeneous distribution in the trimetallic sulphides. The EXAFS results for the trimetallic catalysts are consistent with the presence of nickel or cobalt sulphide domains, and Mo1-xWxS2 solid solutions. The intralayer Mo:W solid solutions were confirmed to be thermodynamically stable with respect to phase separation by DFT calculations, which were also used to aid in the interpretation of the EXAFS results. The effect of the W:Mo ratio on the catalytic properties of the Ni and Co-containing series was found to be different. For the Ni series, increasing the W content caused an activity increase in THN hydrodearomatization (HDA) relative to DBT hydrodesulphurization (HDS), while it had little influence on the relative contribution of the direct desulphurisation (DDS) route with respect to the previous hydrogenation (HYD) route for DBT HDS. In contrast, for the Co series, the activities and selectivities were essentially insensitive to the W content. Both the Ni and Co series of unsupported sulphides were more selective for the HYD route in DBT HDS than a supported NiMo/Al2O3 catalyst. (C) 2016 Elsevier B.V. All rights reserved.