Rhombohedrally　crystallized　three-dimensionally　ordered　macroporous　(3DOM)　perovskite-type　oxides　LaMnO3　with　mesoporous　skeletons　were　prepared　using　the　poly(ethylene　glycol)　(PEG)-　and/or　l-lysine-assisted　poly(methyl　methacrylate)　(PMMA)-templating　method.　Physicochemical　properties　of　the　materials　were　characterized　by　numerous　analytical　techniques.　Catalytic　performance　of　the　as-prepared　LaMnO3　samples　was　evaluated　for　the　combustion　of　toluene.　It　is　found　that　addition　of　appropriate　amounts　of　PEG400　and　l-lysine　was　beneficial　for　the　generation　of　high-quality　3DOM-structured　LaMnO3　(denoted　as　LaMnO3-PL-1,　LaMnO3-PL-2,　and　LaMnO3-PL-3　derived　with　a　PEG400/l-lysine　molar　ratio　of　1.23,　0.61,　and　0.31,　respectively)　with　mesoporous　skeletons　and　high　surface　areas　(32-38m2/g).　Among　the　LaMnO3　samples,　the　LaMnO3-PL-2　one　possessed　the　largest　surface　area　and　the　highest　contents　of　surface　Mn4+　and　adsorbed　oxygen　species.　3DOM-structured　LaMnO3　showed　better　low-temperature　reducibility　than　bulk　LaMnO3,　with　the　LaMnO3-PL-2　sample　displaying　the　best　low-temperature　reducibility.　Under　the　conditions　of　toluene　concentration=1000ppm,　toluene/O2　molar　ratio=1/400,　and　space　velocity=20,000mL/(gh),　the　porous　LaMnO3　catalysts　remarkably　outperformed　the　nonporous　bulk　counterpart;　over　the　best-performing　LaMnO3-PL-2　catalyst,　the　temperatures　required　for　toluene　conversion=50　and　90%　were　ca.　226　and　249°C,　respectively.　The　apparent　activation　energies　(58-61kJ/mol)　for　toluene　combustion　over　the　LaMnO3-PL-1-3　catalysts　were　much　lower　than　that　(97kJ/mol)　over　the　bulk　LaMnO3　catalyst.　It　is　concluded　that　the　large　surface　area,　high　oxygen　adspecies　content,　good　low-temperature　reducibility,　and　unique　bimodal　pore　structure　were　responsible　for　the　good　performance　of　3DOM-architectured　LaMnO3　with　mesoporous　skeletons　for　toluene　combustion.　©　2012　Elsevier　B.V.