AbstractA series of 3D interpenetrating metal‐organic frameworks, namely, [Zn3(BPDC)3(4‐BPT)1.5]·1.5DMF [1, BPDC = biphenyl‐4,4′‐dicarboxylic acid, 4‐BPT = 4‐amino‐3,5‐bis(4‐pyridyl)‐1,2,4‐triazole, DMF = dimethylformamide], [Zn3(BPDC)3(4‐PYTZ)1.5]·1.5DMF [2, 4‐PYTZ = 3,6‐bis(pyridin‐4‐yl)‐1,2,4,5‐tetrazine], [Zn2(OBA)2(4‐PYTZ)]·2DMF [3, OBA = 4,4′‐oxybis(benzoate)], [Zn2(OBA)2(3‐PYTZ)·Zn2(OBA)2(DMF)2]·7DMF [4, 3‐PYTZ = 3,6‐bis(pyridin‐3‐yl)‐1,2,4,5‐tetrazine] and [Zn2(OBA)2(3‐BPT)]·2.5DMF [5, 3‐BPT = 4‐amino‐3,5‐bis(3‐pyridyl)‐1,2,4‐triazole] were synthesized by the reaction of Zn(NO3)2·6H2O with various dipyridyl derivatives and rigid or nonrigid aromatic dicarboxylate ligands. These five compounds were constructed by paddle‐wheel‐type coordination of ZnII pairs and mixed ligands, which can be simplified as nodes and linkers to generate a variety of topologies. Compounds 1 and 2 exhibit threefold interpenetrated 6‐connected pcu topology. The interpenetration observed in compounds 1 and 2 is a rare case of heterointerpenetration. The structure of 3 is derived from a 2D double interpenetrated rhombic grid substructure, and is an interesting example of a self‐catenated framework displaying a 6‐connected uninodal framework with a point symbol (44.610.8). Compound 4, which is derived from a crosslinked threefold interpenetrated substructure with pts topology, displays a self‐catenated 4,6‐connected binodal framework with the point symbol (42.62.72) (42.68.7.84). Compound 5 exhibits a self‐catenated 6‐connected structure with rob topology, and with the point symbol (48.66.8). Compounds 1–5 also display varied luminescence properties in the solid state.