Desulfurization for blast furnace gas is one of the keys to achieve ultra-low emissions for the multi-process in the iron and steel industry. The sulfur component in blast furnace gas is mainly organic sulfur-carbonyl sulfur (COS), which is usually removed by the catalytic hydrolysis method with γ-Al2O3 based catalyst, but its hydrolysis activity and antioxidant capacity need to be improved. In this work, three kinds of catalysts with Fe or La as an active component were prepared by the impregnation method. The physical and chemical properties of the catalysts were characterized by ICP, XRD and TPD. The diffusion effect of gas hourly space velocity (GHSV) and particle size on the catalytic hydrolysis of COS were investigated on a fixed bed-gas chromatography combined device. The structure-activity relationship between the physicochemical properties of the catalysts and the hydrolysis activity of COS and the action mechanism of O2 were also analyzed. The results showed that the addition of Fe or La as active components can obviously improve the COS hydrolysis activity on the catalyst, due to the much more alkaline sites on the surface of the γ-Al2O3 based catalyst at conditions of 80℃ and 160000 h-1. The abundant pore structure and suitable pore size can also reduce the internal diffusion resistance of COS and H2S, enhance the mass transfer process of H2S from the catalyst surface to the gas phase. Fe/Al2O3 catalyst can collaboratively remove H2S and simultaneously maintain a high hydrolytic activity. But the presence of O2 enhanced the adsorption of H2S on the catalyst surface and the sulfidation reaction between H2S and metal Fe. While La/Al2O3 catalyst had better activity and stability for COS hydrolysis, and the active component La can significantly improve the desorption of H2S from the catalyst surface to the gas phase, and then improve the anti-oxygen toxicity ability of the catalyst.