The 1.5% Au/Fe2O3 catalysts prepared by an inverse co-precipitation method calcined at different temperatures was characterized by XRD, XPS, TEM, BET, and tested by CO selective oxidation in H2-rich gas. The results show that the chemical composition and activity of the catalysts are greatly changed with the variation of calcination temperature. The catalyst Au/Fe2O3 calcined at 200℃, highly dispersed particles with the partially oxidized gold species on the support with the mean diameter of 3nm~5nm, displayes the best activity and selectivity of CO selective oxidation. However, the catalytic activity of Au/Fe2O3 decreases drastically with increasing calcination temperature due to the aggregation of metallic gold and bigger particle sizes. It is found that the catalytic behavior is related to the gold particle size but the nature of the support. On the basis of characterization data, in addition to the particle size of metallic gold, the oxidation states of gold are proven to be important for CO selective oxidation in H2-rich gas.