The Co/CexZr1-xO2 catalysts were prepared by the impregnation method and characterized via BET, NH3-TPD, XRD, H-2-TPD, H-2-TPR, TEM and TG-DSC techniques. The study showed that the Co3O4 crystallites had better dispersion on the cubic fluorite CexZr1-xO2 supports compared with on the ZrO2 and CeO2, and the Co/Ce0.6Zr0.4O2 retained the cubic fluorite structure after the reaction. The Ce0.6Zr0.4O2 catalyst showed good catalytic performance, which was attributed to the alkalescence of support surface, better dispersion of active species, better textural property and reducibility. The deposition carbon over the Co/Ce0.6Zr0.4O2 catalyst mainly existed in the form of low-temperature carbon. (C) 2013 Elsevier B.V. All rights reserved.