Emissions of SO₂ from flue gas and marine transport have detrimental impacts on the environment and human health, but SO₂ is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO₂ in a porous material, [Cu₂(L)] (H₄L = 4',4‴-(pyridine-3,5-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO₂ uptake of 17.5 mmol g^-1 at 298 K and 1.0 bar, and the SO₂ binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO₂ to open Cu(II) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO₂ binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO₂ from simulated flue gas mixtures, as confirmed by breakthrough experiments.