The present work provides the basis to obtain three-dimensional (3D) extended porous supramolecular assemblies named supramolecular metal–organic frameworks (SMOFs). This goal can be achieved by considering three key factors: (i) the use of rigid building units, (ii) the establishment of predictable and rigid synthons between the building units, and (iii) the non-coplanarity of functional groups involved in the predictable synthons. Throughout this report we demonstrate the suitability of this synthetic strategy supported by six new SMOFs based on metal-nucleobase entities which fulfill the stated requirements: [Co(ThioG)3] (SMOF-4; ThioG = thioguaninato), [Co(Hade)2X2] (SMOF-5, SMOF-6; Hade = adenine and X = Cl–, Br–), [Cu8(μ3-OH)4(μ4-OH)4(ade)4(μ-ade)4(μ-Hade)2] (SMOF-7; ade = adeninato), [Cu4(μ3-ade)4(μ-ade)2(pentylNH2)2(CH3OH)2(CO3)2(H2O)2] (SMOF-8; pentylNH2 = 1-pentylamine), and [Cu2(μ-ade)2(ade)(μ-OH)(H2O)(CH3OH)]n (SMOF-9). SMOF-4 is built up from monomeric entities in which bidentate thioguaninat...