This study focuses on the synthesis of NiMo-based catalysts in both bulk and coated forms, using ion-exchangeable silica-doped hydrous titanium oxide (HTO:Si) supports. These catalysts were evaluated and compared against commercial NiMo-based catalysts (Amocat 1C and Shell 324) with respect to the hydrogenation of pyrene and the hydrodesulfurization/hydrodenitrogenation of coal-derived liquids. For pyrene hydrogenation, both bulk and supported (coated) NiMo/HTO:Si catalysts performed better than commercial benchmark catalysts on either a catalyst weight or an active metals basis. For both hydrodesulfurization and hydrodenitrogenation of coal-derived liquids in a trickle-bed reactor, the supported and bulk forms of the NiMo/HTO:Si catalysts nearly equalled the overall performance of the commercial catalysts at 3.45, 6.89 and 10.3 MPa and were superior on a total active metals basis. Extensive catalyst characterization was performed to explain the enhanced activity of the NiMo/HTO:Si materials.