In this Letter we describe the synthesis and characterization of a new multiporous crystalline framework based on meso-tetra-(2-quinolyl)-porphyrin, that presents crystal channels adequate for CO 2 reversible sequestering, from 1 to 5 bar of CO 2 pressures. This behaviour is very different from the parent meso-tet-raphenyl-porphyrin, which points to an important favourable interaction of CO 2 with meso-substituted nitrogen aromatic porphyrin free bases.