Three-dimensionally ordered macroporous (3DOM) and bulk Co3O4, Eu0.6Sr0.4FeO3 (ESFO), and 3 wt% Co3O4/Eu0.6Sr0.4FeO3 (3Co(3)O(4)/ESFO) were fabricated using the PMMA-templating (3DOM-Co3O4 and 3DOM-ESFO), citric acid-assisted hydrothermal (Co3O4-bulk and ESFO-bulk), and incipient wetness impregnation (3Co(3)O(4)/3DOM-ESFO and 3Co(3)O(4)/ESFO-bulk) methods, respectively. Physicochemical properties of these materials were characterized by means of various techniques, and their catalytic activities were evaluated for toluene combustion. Compared to the nonporous Co3O4 and ESFO samples, the 3DOM-Co3O4, 3 DOM-ESFO, and 3Co(3)O(4)/3DOM-ESFO samples exhibited higher oxygen adspecies concentrations and better low-temperature reducibility. The 3Co(3)O(4)/3DOM-ESFO sample showed the best catalytic activity for toluene combustion, giving the T-50% and T-90% of 251 and 269 degrees C at 20,000 mL/(g h), respectively. The apparent activation energies of these samples were in the range of 72-88 kJ/mol. We believe that the higher oxygen adspecies concentration, better low-temperature reducibility, and synergistic action between Co3O4 and 3DOM-structured ESFO were responsible for the excellent catalytic performance of 3Co(3)O(4)/3DOM-ESFO. (c) 2012 Elsevier B.V. All rights reserved.