In this work, a Mo2C catalyst that was supported on commercial carbon nanofibers (CNF) was synthetized and tested in the hydrodeoxygenation (HDO) of guaiacol. The effects of operating conditions (temperature and pressure) and reaction time (2 and 4 h) on the conversion of guaiacol and products selectivity were studied. The major reaction products were cresol and phenol, followed by xylenols and toluene. The use of more severe operating conditions during the HDO of guaiacol caused a diversification in the reaction pathways, and consequently in the selectivity to products. The formation of phenol may have occurred by demethylation of guaiacol, followed by dehydroxylation of catechol, together with other reaction pathways, including direct guaiacol demethoxylation, and demethylation of cresols. X-ray diffraction (XRD) analysis of spent catalysts did not reveal any significant changes as compared to the fresh catalyst.