Nanostructured Ni-containing spinel oxide catalysts were obtained using a nanocasting method. Analyses by XRD, TEM, TPD-CO2 and TPR showed that Ni degrees and/or Co degrees entities with high accessibility to CH4 and CO2 were responsible for high catalytic performance in the dry reforming of methane. The NiCo (Co degrees and Ni degrees dispersed on NiAl2O4) and NiAl (Ni degrees dispersed on NiAl2O4) species were highly active for CH4 conversion, whereas Ni degrees dispersed on either Fe3O4-Co3O4 or CeO2-NiAl2O4 provided a lower catalytic performance due to active phase degradation. The higher activity exhibited by NiAl compared to NiCo was related to the higher activity of nickel for CO2 decomposition, while its remarkable stability seemed to be due to the presence of well dispersed nanoparticles involved in long-term conversion because they produced non-deactivating carbon deposits, as suggested by Raman analyses. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.