The catalytic activity of TiO2 nano-particles, prepared by a sol-gel method, was studied when added in the reaction between SO2 and CaO. The reaction products were analyzed by infrared spectrophotometry (IR) and specific surface area analysis and the kinetics and mechanisms of the sulfation catalyzed by the addition of TiO2 are discussed. The results indicate that nano-TiO2, which serves as an active catalytic center, enhances O-2 transfer and is helpful in the diffusion of SO2 from the product layer to the inner unreacted CaO. As a result, the desulfurization efficiency increased. The results also suggest that the SO2 and NO must both be removed simultaneously in order to keep the sulfation rate. The desulfurization reactions are first order for SO2 concentration and zero order for O-2 concentration and include two zones, the surface reaction zone and the product layer diffusion zone, with later being the rate limiting step. The apparent activation energy of the desulfurization reaction decreased with the addition nano-TiO2 as compared to that without. The unreacted shrinking reaction core model was used to investigate the reaction kinetics and was shown to describe the course of desulfurization. Lastly, the results obtained through calculation agree with the empirical data. (C) 2011 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.