The adsorptive properties of the isoreticular series [Ni8(OH)4(H2O)2(BDP_X)6] (H2BDP_X = 1,4-bis(pyrazol-4-yl)benzene-4-X with X = H (1), OH (2), NH2 (3)) can be enhanced by postsynthetic treatment with an excess of KOH in ethanol. In the case of X = H, NH2, this treatment leads to partial removal of the organic linkers, deprotonation of coordinated water molecules and introduction of extraframework cations, giving rise to materials of K[Ni8(OH)5(EtO)-(H2O)2(BDP_X)5.5] (1@KOH, 3@KOH) formulation, in which the original framework topology is maintained. By contrast, the same treatment with KOH in the [Ni8(OH)4(H2O)2(BDP_OH)6] (2) system, enclosing the more acidic phenol residues, leads to a new material containing a larger fraction of missing linker defects and extra-framework cations as well as phenolate residues, giving rise to the material K3[Ni8(OH)3(EtO)(H2O)6(BDP_O)5] (2@KOH), which also conserves the original face cubic centered (fcu) topology. It is noteworthy that the introduction of missing linker defects leads to a higher accessible pore volume with a concomitant increased adsorption capacity. Moreover, the creation of coordinatively unsaturated metal centers, charge gradients, and phenolate nucleophilic sites in 2@KOH gives rise to a boosting of CO2 capture features with increased adsorption heat and adsorption capacity, as proven by the measurement of pulse gas chromatography and breakthrough curve measurements of simulated flue gas.