Ordered mesoporous silicate SBA-15 and Ti-SBA-15 (Si/Ti = 10) and mesoporous aluminosilicate MAS (Si/Al = 20) supports were prepared by a hydrothermal method. Peptization of gamma-alumina with these supports was carried out with 2% acetic acid, and the resulting composite materials were loaded with 3 wt % NiO and 10 wt % MoO3 by a simple impregnation method. The physicochemical properties of these catalysts were examined with the following techniques, such as XRD, N-2 sorption, diffuse reflectance UV vis spectra, TEM, H-2-TPR, NH3-TPD, and H-2 chemisorption. Ti and Al incorporated supported catalysts strongly influence the hydrodeoxygenation (HDO) activity of guaiacol, investigated in a fixed-bed down-flow quartz reactor at atmospheric pressure. The MoO3-NiO/MAS supported catalyst shows maximum conversion compared to MoO3-NiO/Ti-SBA-15 and MoO3-NiO/SBA-15. gamma-Alumina composite catalysts displayed an improved HDO activity attributed to an increased acidity and dispersion of active sites.