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.