Sulphur hexafluoride is a highly potent greenhouse gas that is commonly used as insulation in high voltage applications or in the manufacture of electronics. As a greenhouse gas, SF6 is not as well-known to the general public as CO2, but yet its global warming potential is over 23,000 times that of CO2. Point sources of SF6 emissions include electronics factories or high voltage equipment, and there is a need to reduce the emissions of this potent greenhouse gas into the atmosphere. We demonstrate that metal-organic frameworks (MOFs) are promising SF6 sorbents that can effectively capture SF6 from a gas mixture containing N2. Tailoring the pore size of MOFs is an effective way to increase both the SF6 selectivity and uptake. Mixed-linker ZIF-7-8, UU-200, CTH-18 are some examples of MOFs that show good selectivity and uptake towards SF6 due to their optimal pore size. In addition, the novel gallium 1,2,4,5-tetrakis(4-carboxyphenyl)benzene (TCPB4−) MOF (Ga-TBAPy) has suitable pore dimensions (5.2 × 8.4 Å and 5.3 × 10 Å) to take up 2.25 mmol g−1 of SF6 at 10 kPa and an excellent SF6-over-N2 selectivity of over 400. Ga-TCPB also has high chemical stability in aqueous and acidic media as well as in organic solvents. MOFs have promising properties that can aid in mitigating the global warming contributions from the emission of SF6.