Catalysts supported on carbon materials, with different structures: activated carbon (AC), graphite (G) and three types of carbon nanofibers (CNF) with different structures with respect to the arrangement of the graphitic planes (platelet (CNF-P), fishbone (CNF-F) and ribbon (CNF-R)) were prepared by the following methods: impregnation and gold-sol. CNF were synthesized by a chemical vapour deposition (CVD) method using C2H4 as the carbon precursor and Ni/SiO2 as the catalyst. Different techniques were employed to characterize both the supports and the final Au catalysts: atomic absorption spectrometry, transmission electron microscopy (TEM), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), Raman spectroscopy, elemental analyses (CNH), N-2 adsorption-desorption analysis, temperature-programmed reduction (TPR) and temperature-programmed decomposition (TPD), which have established distinct morphological, graphitic and porous characteristics. Both the crystalline nature of the carbon supports and the preparation method had a strong influence on the way in which Au particles were deposited on the carbonaceous supports. The higher the crystallinity and the smaller the particle size, the higher the activity and selectivity of the catalysts in the liquid-phase oxidation of glycerol. The following sequence in the catalytic activity was observed in terms of TOF (min(-1)): Au/G-SGT (0.07) > Au/CNF-R-SGT (0.067) > Au/G-IMP (0.053) > Au/CNF-F-SGT (0.052) > Au/CNFP-SGT (0.051) > Au/AC-SGT (0.049) > Au/CNF-R-IMP (0.047)> Au/AC-IMP (0.045) > Au/CNF-F-IMP (0.040) > Au/CNF-P-IMP (0.036). (C) 2011 Elsevier B.V. All rights reserved.