To accelerate the green and low-carbon development of the steel industry, it is urgent to remove sulfur compounds from blast furnace gas. COS is the highest sulfur containing pollutant in blast furnace gas, and catalytic hydrolysis is the most common method for removing COS. This study mainly introduces from three aspects. Firstly, it explores the effects of three different morphologies of CeO2 (rod-shaped, cubic, and spherical) on the performance of COS removal. The characterization of the catalyst shows that the (110) crystal surface of rod-shaped ceria is more prone to generating oxygen vacancies and has the strongest alkaline sites, which is most conducive to the removal of COS. Secondly, the improvement of COS removal performance by La doped CeO2 was investigated, resulting in an increase in desulfurization stability from 240 minutes to 570 minutes and a desulfurization rate increase of about 60%, indicating that La doping has a promoting effect on the desulfurization performance of the catalyst. Finally, the effects of the number and strength of alkaline sites on catalytic activity were jointly demonstrated through characterization such as CO2-TPD, XPS, and EPR. The introduction of oxygen vacancies in metal oxides promoted the activation and dissociation of H2O, and the formation of hydroxyl groups promoted the hydrolysis activity of COS. Among them, having a large specific surface area of CeO2-R may be beneficial for exposing more surface active sites, facilitating the adsorption of CO2 and generating more alkaline sites. On the other hand, CeO2 doped with lanthanum metal generates more oxygen vacancies due to the interaction between metals, promoting the activation and dissociation of H2O to form more hydroxyl groups, which will contribute to the hydrolysis activity of COS; Finally, the sulfate deposited on the surface of the catalyst is the main cause of catalyst deactivation.