The　three-dimensional　(3D)　macroporous　orthorhombically　crystallized　perovskite-like　oxides　La2CuO4　were　prepared　using　the　polymethyl　methacrylate　(PMMA)　microsphere-templating　strategy　with　nitrates　of　lanthanum　and　copper　as　metal　source　and　a　mixed　solution　of　methanol　and　ethylene　glycol　as　solvent　in　the　absence　or　presence　of　citric　acid　and　after　calcination　at　various　atmospheres.　The　as-prepared　materials　were　characterized　by　means　of　X-ray　diffraction,　N-2　adsorption-desorption,　scanning　electron　microscopy,　X-ray　photoelectron　spectroscopy,　and　hydrogen　temperature-programmed　reduction.　Catalytic　activities　of　the　materials　were　evaluated　for　the　combustion　of　methane.　The　catalyst　(La2CuO4-1)　prepared　with　PMMA　and　citric　acid　possessed　a　3D　ordered　macroporous　(3DOM)　structure　and　a　surface　area　up　to　46　m(2)/g,　whereas　the　one　(La2CuO4-2)　prepared　with　PMMA　but　without　citric　acid　exhibited　a　3D　wormhole-like　macroporous　structure　and　a　surface　area　of　39　m(2)/g.　There　was　the　presence　of　a　trace　amount　of　La2O2CO3　phase　in　the　La2CuO4-1　and　La2CuO4-2　catalysts.　The　calcination　procedure　(first　in　N-2　flow　at　700　degrees　C　and　then　in　air　flow　at　300　and　800　degrees　C,　respectively)　was　crucial　in　forming　the　3D　porous　structure　of　La2CuO4.　The　as-obtained　catalysts　had　overstoichiometric　oxygen.　The　La2CuO4-1　catalyst　showed　better　low-temperature　reducibility　than　the　La2CuO4-2　and　La2CuO4-Citrate　(derived　from　the　conventional　citric　acid-complexing　route)　catalysts.　The　3D　porous　La2CuO4　materials　performed　well　in　catalyzing　the　oxidation　of　methane,　with　the　La2CuO4-1　catalyst　showing　the　best　performance　(the　temperature　for　90%　CH4　conversion　=　672　degrees　C　(reaction　rate　=　ca.　40　mmol/(g　h))　at　CH4/O-2　molar　ratio　=　1/10　and　space　velocity　=　50,000　mL/(g　h).　It　is　concluded　that　the　excellent　catalytic　performance　of　La2CuO4-1　was　mainly　related　to　the　higher　surface　area,　better　low-temperature　reducibility,　and　3DOM　architecture.　(C)　2011　Elsevier　B.V.　All　rights　reserved.