Abstract: | Metallosupramolecule‐based polymeric platforms with high degrees of hierarchy and tailorable functionalities are of great interests because of their unique morphologies and potential applications. Herein, the controllable synthesis of a highly‐ordered polymeric structure, {M,P‐Co8(PDA)6(HIP)3(DMF)5(H2O)]3‐Co(DMF)(H2O)2]} ( 1 ) (PDA=2,6‐pyridinedicarboxylate, HIP=5‐hydroxyisophthalate, DMF=dimethylformamide) with unique topology is reported. The solid‐state structure of 1 reveals that it is alternately and periodically assembled from racemic supramolecular monomers to form a zigzag‐shaped polymeric strand. Discrete racemic supramolecules ( 2 ) with topologies similar to those of monomeric species of 1 are also controllably synthesized in a separate reaction. Formation of intermolecular hydrogen bonds between supramolecules associated with hydroxyl groups of HIPs are critical for the unique solid‐state packing geometries of 1 and 2 . |