To achieve maximum yield from bifunctional catalysts in slurry-phase hydrocracking of heavy oil, an appropriate balance between the acidic and hydrogenating functions of the catalyst is required. In this study, the bifunctional behavior of MoS2-amorphous silica–alumina (ASA) catalysts was investigated by varying the number of Brønsted acid sites (ηH+) and MoS2edge sites (ηMo) associated with ASA and MoS2, respectively. Using a model feed consisting of phenanthrene and decalin, we report evidence of bifunctional catalysis for MoS2-ASA catalysts with ηH+/ηMo ratios between 3.1 and 15.5. Deviations from bifunctional behavior were also observed: at a low ηH+/ηMo ratio (0.39), phenanthrene hydrogenation was preferred, whereas at the highest ηH+/ηMo ratio (30.9), acid-catalyzed reactions dominated and promoted coke formation that resulted in catalyst deactivation. Considering that the in situ formation of MoS2blocked some acid sites on the ASA, we introduced a new parameter that quantified the number of Brønsted acid sites available in the reactor system (ηH+c). We show that the total product yield correlated with ηH+cand that the maximum yield occurred for the catalyst with the highest ηH+c.