Two different types of macroporous and mesomacroporous carbons have been synthesized using the templating method with polystyrene (PS) and SBA-15/PS (1:4) as templates. These synthesized carbon materials were exact replicas of the templates and showed a small window in the large pores of macroporous carbon in addition to mesophase in mesomacroporous carbon. Materials were characterized using X-ray diffraction (XRD), nitrogen adsorption-desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared (FT-IR), and CO chemisorption. Mo, Co, and CoMo catalysts were prepared by supporting the aforementioned metals on optimized macroporous and mesomacroporous carbon, while commercial activated carbon (Darco G-60) and alumina (gamma-Al2O3) supported catalysts were used for comparison purposes. Thiophene hydrodesulfurization of these catalysts showed that mesomacroporous carbon supported catalysts had superior activity and selectivity compared to the others, which might be due to its better metal dispersion and bimodal porosity which made transport easier and minimized channel blocking.