CuO/γ-Al2O3 sorbents were prepared by means of impregnation. Thermogravimetric technique was used to study the sulfation of CuO/γ-Al2O3 sorbents. The sulfation tests were performed using gas containing 0.1%-0.9% SO2, 5% O2, 3% H2O steam, and N2 as the balance. Experimental conditions including temperature, SO2 concentration and pore structure were studied. The sulfation experiment results show that the sulfation reaction rate increases with increasing temperature and SO2 concentration, and the surface and pore volume decrease after sulfation. Sulfation kinetics analysis shows that the reaction between CuO/γ-Al2O3 and SO2 obeys pore-blocking model well. Proportionality (pore-blocking constant) 1/λ decreases with increasing temperature. The activation energy and reaction order with respect to SO2 obtained are 37.9 kJ/mol and the first order, respectively. The existing state of CuO exerts an influence on activation energy.