Metal–organic frameworks (MOFs) have extremely high surface areas and pore volumes, tunable pore sizes and chemical functionalities and are an interesting addition to the field of porous materials. One of the key challenges that needs to be overcome to elevate MOFs to the applied level is their sensitivity to humid environments. The work reported here seeks to address this critical issue by examining two important contributors to MOF stability or instability: basicity (pKa value) of the pillar ligand and catenation of the framework. Catenation is the interpenetration or interweaving of two or more identical and independent frameworks. We demonstrate that, using catenation in combination with a pillaring strategy, it is possible to obtain water stable MOFs even when the pillar ligand has lower basicity (pKa value). This study shows that after 90% relative humidity (RH) exposure, comparing Zn-BDC-DABCO (DMOF) and Zn-BDC-BPY (MOF-508), MOF-508 is stable due to its two-fold interpenetration that prevents significant water adsorption. In contrast, comparing non-catenated isostructural pillared MOFs Zn-TMBDC-DABCO (DMOF-TM) and Zn-TMBDC-BPY (MOF-508-TM), MOF-508-TM is unstable since BPY is less basic (higher pKa) and less rigid than DABCO.