Three-dimensionally ordered macroporous (3DOM) Eu0.6Sr0.4FeO3-supported cobalt oxide nanocatalysts (yCoO(x)/3DOM-ESFO; y wt% = 1, 3, 6, and 10) were prepared using the incipient wetness impregnation method. Physicochemical properties of the composite materials were characterized by means of numerous techniques, and their catalytic performance was evaluated for the combustion of toluene. It is shown that all of the samples displayed a well-defined 3DOM architecture with a surface area of 22-31 m(2) g(-1) and the loaded cobalt oxide nanoparticles with a diameter of 7-11 nm were well dispersed on the surface of the 3DOM-ESFO support. Among the yCoO(x)/3DOM-ESFO samples, the 3CoO(x)/3DOM-ESFO and 6CoO(x)/3DOM-ESFO ones possessed the highest oxygen adspecies concentration and the best reducibility at low temperature, and hence showing the best catalytic performance (the temperatures required for 50 and 90% toluene conversions were ca. 250 and 270 degrees C at a space velocity of 20,000 mL g(-1) h(-1), respectively) for toluene combustion. The apparent activation energies (ca. 72 kJ mol(-1)) of 3CoO(x)/3DOM-ESFO and 6CoO(x)/3DOM-ESFO were lower than that (81 kJ mol(-1)) of 3DOM-ESFO. It is concluded that the enhanced catalytic performance of 3CoO(x)/3DOM-ESFO and 6CoO(x)/3DOM-ESFO for toluene combustion was mainly related to their higher oxygen adspecies concentrations, stronger reducibility at low temperature, and better dispersion of cobalt oxide nanoparticles. (C) 2012 Elsevier B.V. All rights reserved.