Due to its toxicity and corrosiveness, it is of enormous significance to efficiently capture and recover sulfur dioxide (SO2) from flue gas and natural gas. Herein, a new type of IL/MIL-0.7 composite was precisely designed to meet this challenge, which exhibits a high adsorption capacity for SO2 (13.17 mmol·g-1) at 298 K and 1 bar while excludes almost completely carbon dioxide (CO2) (0.27 mmol·g-1) and nitrogen (N2) (0.07 mmol·g-1). The high IAST selectivity (at least 11925) of IL/MIL-0.7 for SO2/CO2 can be achieved within the whole test pressure range. In addition, the breakthrough experiment also confirmed the excellent performance of the composite for deep removal of 2000 ppm SO2. Furthermore, the IL/MIL-0.7 composites can maintain excellent performance after four adsorption and desorption circulations and the thermostability can up to ~450 K. Therefore, this stable IL@MOF composite has the potential application as an effective adsorbent for SO2 removal from flue gas.