There is an urgent need to address sulfur dioxide (SO2) from the burning of fossil fuels, which poses a serious hazard to the surrounding environment due to its emission. In this work, UiO-66-type metal–organic framework materials (MOFs) were prepared by hydrothermal method and applied to flue gas desulfurization. Through characterization analysis, it was found that UiO-66 sample had high crystallinity and good thermal stability. Besides, UiO-66 sample had a large specific surface area (1423 m2/g) and a large pore volume (0.69 cm3/g). In the desulfurization experiments of SO2/CO2/O2/N2 gas mixture (0.3/10.0/5.5/84.2 vol.%), UiO-66 had a breakthrough time of 137.6 min/g for SO2, the high selectivity of SO2/CO2 (36.0), and strong acid resistance. Besides, the adsorption thermodynamic analysis can confirm that the adsorption process of UiO-66 for SO2 was a combination of physical adsorption and chemical adsorption. At 1.0 bar and 298 K, the adsorption capacity of SO2 on UiO-66 reached 8.12 mmol/g.