A robust, noncatenated, and permanently microporous metal−organic framework (MOF) material has been synthesized by combining a new nonplanar ligand, 4,4′,4′′,4′′′-benzene-1,2,4,5-tetrayltetrabenzoic acid, with a zinc(II) source under solvothermal conditions. The new material features cavities that are readily modified via activation and functionalization of framework nodes (as opposed to struts). A preliminary investigation of the “empty cavity” version of the material and six cavity-modified versions reveals that modification can substantially modulate the MOF’s internal surface area, pore volume, and ability to sorb molecular hydrogen.