A series of Ni-substituted barium hexaaluminate catalysts, Ba0.75NiyAl12-yO19-delta (y = 0.4, 0.6 and 1.0), were tested for CO2 reforming of CH4 at temperatures between 200 and 900 degrees C. Temperature programmed surface reaction results show that the reaction lights-off in a temperature range between 448 and 503 degrees C with a consistent decrease in light-off temperature with increasing Ni substitution. Isothermal runs performed at 900 degrees C show near equilibrium conversion and stable product concentrations for 18 h on all catalysts. Temperature programmed oxidation of the used catalysts show that the amount of carbon deposited on the catalyst increases with Ni substitution. High resolution XRD of the used Ba0.75Ni0.4Al11.6O19-delta catalyst shows a statistically significant contraction of the unit cell which is the result of NiO reduction from the lattice. XRD of the used catalyst also confirms the presence of graphitic carbon. XPS and ICP measurements of the as prepared catalysts show that lower levels of Ni substitution result in an increasing proportion of Ba at the surface. Published by Elsevier B.V.