A new functionalization technique, solvent-assisted ligand incorporation (SALI), was developed to efficiently incorporate carboxylate-based functionalities in the Zr-based metal–organic framework, NU-1000. Unlike previous metal node functionalization strategies, which utilize dative bonding to coordinatively unsaturated metal sites, SALI introduces functional groups as charge compensating and strongly bound moieties to the Zr₆ node. Utilizing SALI, we have efficiently attached perfluoroalkane carboxylates of various chain lengths (C₁–C₉) on the Zr₆ nodes of NU-1000. These fluoroalkane-functionalized mesoporous MOFs, termed herein SALI-n, were studied experimentally and theoretically as potential CO₂ capture materials.