In comparison to the vast field of porous materials, research into hydrogen-bonded organic frameworks (HOFs)and especially the subclass of metal hydrogen-bonded organic frameworks (M-HOFs), with only very few structures showing permanent porosity thus faris still in its infancy. Herein, Kuratowski coordination units, which are well-known from various complexes and metal–organic frameworks, were applied to advance this field of research with the synthesis and characterization of a novel series of M-HOFs. Synthesis of Kuratowski complexes with the 1H-benzotriazole-5,6-diamine (H-btda) ligand resulted in molecular building blocks, which initially assemble into CFA-20-Cl and CFA-20-Br M-HOFs ((2,6-lutidinium)+[Zn5X4(btda)6X]−·n(DMF); X = Cl, Br; CFA-20 = Coordination Framework Augsburg University-20, DMF = N,N-dimethylformamide). Both frameworks are isostructurally stabilized via a unique hydrogen bond framework between 12 amine functional groups of six btda ligands and a central 12-fold hydrogen bonded halogen anion, which adapts the coordination of an irregular icosahedron. Postsynthetic ligand exchange at the Kuratowski complex of CFA-20-Cl performed with Tp and Tp* ligands resulted in permanently porous CFA-20-Tp and CFA-20-Tp* M-HOFs ([Zn5Y4(btda)6]; Y = Tp (trispyrazolylborate), Tp* (tris­(3,5-dimethyl-1-pyrazolyl)­borate)), which, thus, constitute an important addition to the meager subclass of permanently porous M-HOFs. Crystallization of the soluble complex of CFA-20-Tp* from dimethylsulfoxide (DMSO) was additionally shown to result in a variant CFA-20-Tp*-DMSO M-HOF structure.