Direct conversion of MoO3 to cubic molybdenum carbides by temperature-programmed reaction (TPR) with a reacting gas mixture of H-2/toluene has been studied at 673 K. We report for the first time that the MoO3 precursor is able to produce a cubic molybdenum carbide phase which seems to have molybdenum vacancies in the cubic structure and such vacancies affect the experimental intensity ratio of the signals (1 1 1) and (2 0 0) of the X-ray powder diffraction patterns of the prepared material, this observation is backed up by simulation of the X-ray powder diffraction patterns of the defective structure and also because of the lower unit cell size of the material prepared (0.4097 +/- 0.0005 nm). It is possible to increase the degree of conversion of the MoO3 to the cubic carbide phase by pressing at 379 bar the original precursor inducing preferred orientations of the crystallographic planes (0 2 0), (0 4 0) and (0 6 0) which facilitate the carburization of the oxide by precluding the formation of MoO2 structures. Molybdenum carbides produced were found to be active for the low temperature hydrogenation of toluene. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.