Pechini route [US Patent No. 3,330,697 (1967)] was used for supporting perovskite-like systems on thin-wall corundum honeycomb support to prepare catalysts for high-temperature processes of methane combustion and selective oxidation into syngas. In this preparation, the surface of corundum monoliths walls was shown to be covered by strongly adhering porous perovskite layer formed by rounded crystals. At high temperatures when pore diffusion is expected to affect catalysts performance in fast reactions, this spatial distribution of the active component could be attractive. In the kinetically controlled region of methane oxidation, samples prepared via Pechini route possess activity comparable with that of samples made via support wet impregnation with mixed nitrate solutions, when an active component is uniformly distributed across the wall thickness. Corundum-supported lanthanum manganite and ferrite are the most active in the reaction of methane combustion, while its selective oxidation into syngas effectively proceeds on supported lanthanum cobaltite and nickelates. Corundum-supported perovskites are more thermally stable as compared with those on gamma-alumina support.