Sequence SO2/CO2 capture technology will be more attractive as the control on secondary pollution is strengthened and the operating cost is decreased. The sulfation, pore, and fractal characteristics of a spent CaO‐based adsorbent are studied. The spent modified CaO/Ca12Al14O33 is used in this study. The effect of cyclic numbers in the calcium‐looping process on sulfation conversion and the pore characteristics of spent adsorbents is investigated. A model between the fractal dimension and the Brunner–Emmet–Teller (BET) specific surface area (SBET) of the spent CaO/Ca12Al14O33 is established. The sulfation reaction characteristic of spent adsorbents is also interpreted by the fractal mechanism. Results show that the sulfation conversions of spent CaO/Ca12Al14O33 are almost 10% higher than those of spent CaO at the same cyclic number. The sulfation reaction rate in the product layer diffusion‐controlled stage is much lower than that in the chemical reaction‐controlled stage. The spent CaO/Ca12Al14O33 adsorbents are mainly composed of meso‐ and macropores. The pore size distributions show that there are two peaks in the curves. The surface fractal dimension (D1) and the pore fractal dimension values of spent adsorbents show a trend that is similar to those of SBET and total pore volume, respectively. The relation between the D1 values of four different CaO‐based adsorbents and their SBET values is a quadratic function, and a higher D1 indicates an irregular surface of disordered fractals, which significantly affects the efficiency of the sulfation reaction. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd.