The role of the synthesis method of molybdenum carbide nanoparticle catalysts supported on carbon nanofibers on crystal structure and on catalytic performance in hydrodeoxygenation of stearic acid was investigated. We obtained the cubic phase of molybdenum carbide (alpha-MoC1-x) by impregnating carbon nanofibers with a solution of (NH4)(2)MoO4, then exposing them to 20% CH4/H-2 at 650 degrees C for 2 h. When increasing the Mo loading from 7.5 wt% to 20 wt% or using the carbothermal reduction method, i.e. using carbon from the support to reduce the (NH4)(2)MoO4 precursor at 800 degrees C for 6 h, the hexagonal phase (beta-Mo2C) resulted. Experiments with stearic acid hydrodeoxygenation showed that both phases (7.5 wt% Mo) displayed similar intrinsic activities. However, alpha-MoC1-x/CNF reached 80% stearic acid conversion after 240 min while the beta-Mo2C/CNF catalyst attained the same conversion after 360 min. CO chemisorption results showed that alpha-MoC1-x/CNF and beta-Mo2C/CNF have a similar number of potential active sites (66 and 56 mnol g(-1), respectively). We attribute the difference in catalytic performance between alpha-MoC1-x/CNF and beta-Mo2C/CNF to differences in the catalyst's crystal structure, more specifically, the associated site density. The face-centered cubic alpha-MoC1-x/CNF has a lower site density (0.1096 Mo atoms angstrom(-2)) than the hexagonal close-packed beta-Mo2C/CNF (0.1402 Mo atoms angstrom(-2)), making the Mo atoms at the surface of the alpha-MoC1-x phase more accessible for large reactant molecules such as stearic acid thus allowing its convertion in shorter times.