Sulfur hexafluoride (SF 6 ) is widely used as an insulating gas, being an etchant and contrast agent in the electrical, semiconductor, and medical industries. However, due to its long lifetime and high global warming potential in the atmosphere, SF 6 must be carefully handled to prevent leakage during production and usage. Herein, we report a sod-net metal-azolate framework (MAF) named MAF-stu-111, which decorates methyl and aldehyde groups in the porous windows, showing high adsorption affinity for SF 6 at low pressure. Stability tests, gas adsorption, and breakthrough experiments demonstrated that MAF-stu-111 possesses excellent water and chemical stability, fully reversible SF 6 uptake, high SF 6 /N 2 separation selectivity (10:90, 285.2), good reusability, and high SF 6 recovery purity (99.03%). Theoretical calculations revealed that hydrogen atoms of methyl and aldehyde groups can form multiple hydrogen bonds with SF 6 molecules, which ensure that SF 6 molecules are firmly held within the MAF-stu-111 framework, playing a key role in the selective separation of SF 6 /N 2 .