Not only is excellent performance in SO2 capture by porous materials (uptake above 17 mmol g^–1) relevant, but also finding a correlation between the architecture changes into a family and their SO₂ adsorption is very useful. In this contribution, we studied the SO₂ adsorption behavior (at very low pressure) of an Al(III)-MOF family that shares the pore architecture of MIL-53. The results indicate an inversely proportional trend for the SO₂ capture and pore expansion, since by increasing the length of the channel pore, the SO₂ uptake gradually decreases. In addition, this trend is clearly observed in the heat of adsorption, which describes the interaction between the SO₂ molecule and the μ-OH functional group. These finding are supported by experimental analysis and computational studies.