A new method was employed for the preparation of a set of lanthanum cobaltites of general formula La1-xMxCoO3+delta with M=Ce, Eu and x=0O, 0.05, 0.1, 0.2. All the samples thus prepared were nanostructured, thermally very stable and characterised by highly crystalline perovskite-like structure and high surface area. Their activity as catalysts for the catalytic flameless combustion (CFC) of methane was by ca. one order of magnitude higher than that of their analogues, prepared through the usual calcination-milling (CM) procedure. Adsorption of oxygen was accompanied by formation of paramagnetic species. Desorption of preadsorbed oxygen was dependent on the nature of the doping element and on the value of the stoichiometric coefficient x of their formula. A correlation between the temperature of the maximal rate of oxygen release and catalytic activity was found. The following scale of activity for the title reaction versus x values could be set up: 0.1Ce>0.05Ce>0>0.05Eu>0.1 Eu congruent to 0.2Ce. The higher activity of Ce-doped catalysts as compared to those doped with Eu was found to be related to the strength of the bond between oxygen and Co ions.