The effects of pore structure on the reaction rates and selectivities in the liquid-phase hydrogenation of 2-ethylanthraquinone over Ni-B amorphous alloy catalysts prepared by the reductant-impregnation method were studied using regular (HMS, MCM-41, and SBA-15) and commercial mesoporous silicas as supports. The composition, particle size, and location of the Ni-B particles were profoundly influenced by the pore structure of the supports. It is found that the location of the Ni-B particles depended on the pore size of the supports, whereas the uniformity of particle size was related to the interaction between the Ni-B particles and the supports. The hydrogenation rate was much faster on Ni-B catalysts with pore diameters exceeding 5 nm than on the narrow-pore catalysts, whereas the selectivity to 2-ethyldihydroanthraquinone, the carbonyl group hydrogenation product, was higher on Ni-B catalysts supported on regular mesoporous silicas. The best activity and selectivity were achieved when using SBA-15 as the support, which is attributable to the formation of more uniform active sites due to the unique pore structure of SBA-15.