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Anthropogenic greenhouse gas emission poses as serious threat to our environment and it is therefore of utmost importance that efficient systems are developed to mitigate these issues. SF₆, in particular, has attracted more attention in recent years due to its global warming potential which severely exceeds that of CO₂. In this study we present the SF₆ sorption properties of four highly porous 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene-based (TBAPy⁴⁻) metal-organic frameworks containing either ytterbium(III), thulium(III), cerium(III), or hafnium(IV). These MOFs can be synthesized with high crystallinity in as little as 5 h and were found to have good SF₆ uptakes due to their suitable pore size. The SF₆ uptake of the Yb-TBAPy MOF reached 2.33 mmol g⁻¹ with high Henry's law SF₆-over-N₂ selectivity of ∼80 at 1 bar and 293 K. The TBAPy-MOFs were also found to have good chemical stability and good cyclic SF₆ …