Reduction of metal oxide oxygen carrier has been attractive for direct CO oxidation and CO2 separation. To investigate the reduction behaviors of iron oxide prepared by supporting Fe2O3 on gamma-Al2O3 and its effect on CO oxidation, fluidized-bed combustion experiments, thermogravimetric analyzer (TGA) experiments, and density functional theory (DFT) calculations were carried out. Gas yield (gamma(CO2)) increases significantly with the increase of temperature from 693 K to 1203 K, while carbon deposition decreases with the increase of temperature from 743 K to 1203 K, where temperature is a very important factor for CO oxidation by iron oxide. Further, it were quantitatively detected that the interaction between CO and Fe2O3, breakage of O-Fe bonds and formation of new C-O bonds, and effect of reduction degree were quantitatively detected. Based on adsorptions under different temperatures and reducing processes from Fe3+ into Fe2+, Fe+ and then into Fe, it was found that Fe2+ -> Fe+ was the reaction-controlling step and the high oxidation state of iron is active for CO oxidation, where efficient partial reduction of Fe2O3 into FeO rather than complete reduction into iron may be more energy-saving for CO oxidation. (C) 2011 Elsevier B.V. All rights reserved.