Ag represents an interesting dopant for the highly active LaCoO3 perovskites used for the catalytic flameless combustion (CFC) of methane, due to its ability to adsorb and activate oxygen and to the possibility of incorporation into the framework as Ag+ or Ag2+, with formation of oxygen vacancies. In the present work we compared the catalytic activity and resistance to sulphur poisoning of a series of LaCoO3, x%Ag/LaCoO3, La1-xAgxCoO3 samples (nominal composition), the latter two notations indicating post-synthesis Ag loading or direct incorporation during the synthesis, respectively. The samples were prepared by flame pyrolysis (FP) and by the sot-gel (SG) method, leading to different particle size and possibly to different incorporation degree of the dopant, quantified by Rietveld refinement of XRD patterns. Higher activity was observed, in general, with fresh catalysts synthesised by FP. The SG samples demonstrated a slightly better resistance to sulphur poisoning when considering the conversion decrease between the fresh and the poisoned samples, due to lower surface exposure. However, interesting data have been obtained with some of the Ag-doped poisoned FP samples, performing even better than the fresh SG-prepared ones. Ag addition led to a complex change of activity and resistance to poisoning. The activity of FP-prepared samples doped with a small amount of Ag (e.g. 5 mol%) was indeed lower than that of the undoped LaCoO3. By contrast, a further increase of Ag concentration led to increasing catalytic activity, mainly when big extra framework Ag particles were present. By contrast, for SG samples a low Ag amount was beneficial for activity, due to an increased reducibility of Co3+. (C) 2009 Elsevier B.V. All rights reserved.