CoMo additive-impregnated dried catalysts are studied, exploring the “CoMoS” active phase features by combining X-ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and catalytic tests. Starting from different polyoxomolybdate precursors, additive-impregnated dried, additive-free dried and calcined catalyst performances are compared. TEM reveals that the mean particle sizes are about 3.1 nm and do not depend on the catalytic precursors except for the additive-free dried catalysts exhibiting higher lengths: 3.7 nm. XPS quantification of the Mo species shows that 75 mol% of the Mo species are present in the MoS₂ phase whatever the preparation route. This value is slightly enhanced (ca. 85%) with additive impregnation. The molybdenum to aluminium surface coverage ratio (Mo/Al) ranking is found to be as follows: additive-free dried < additive-impregnated dried < calcined. However, this ranking is not significantly modified by the impregnating solution used, and the behaviour is similar for the cobalt to aluminium ratio (Co/Al). A geometrical model combining XPS quantification of the crystallite's Co/Mo ratio and DFT calculations is used to establish a correlation with the catalytic results obtained in toluene hydrogenation. It is shown that the catalytic performances of additive-free dried, additive-impregnated dried and calcined catalysts directly correlate the number of mixed Co–Mo sites present at the MoS₂ edges. DFT calculations highlight that the adsorption step of toluene is thermodynamically favored on the mixed Co–Mo site located at the M-edge. As a consequence, this study suggests that the various routes of preparation leading to different catalytic performances would not lead to new types of active sites or morphology but rather to a different number of mixed sites present at the edges.