The cyclic reaction between CH4 and O-2 over perovskite-type La0.8Sr0.2Fe0.8Co0.2O3-delta, La0.75Sr0.25Fe0.6Co0.15Al0.25O3-delta and La0.8Sr0.2Fe0.8Co0.2O3-delta/gamma-AlO(OH), impregnated with 0.5 wt% Rh or Pt, was studied at 873 K. Synchrotron X-ray and neutron diffraction patterns of La0.75Sr0.25Fe0.6Co0.15Al0.25O3-delta proved a rhombohedral structure with Al distributed over the octahedral B-site. The oxygen non-stoichiometry (delta) was determined by thermogravimetric analysis at 958 K for pO(2) > 10(-22) atm. High selectivity to the partial oxidation products CO and H-2 was observed when 3 - delta was lower than 2.76 and 2.78 for the mentioned oxides, with and without Al, respectively. The role of Rh relates solely to the activation of CH4. A stable high selectivity throughout the pulse sequence was achieved when utilizing partially reduced materials. In situ synchrotron XRD proved that the oxides retained the perovskite structure during the reduction/oxidation cycle, and no phase decomposition occurred. The strong correlation between results from catalytic transient tests and thermogravimetric analysis suggests that the CO selectivity is ruled by the redox potential of the reducible oxide. (C) 2010 Elsevier Inc. All rights reserved.