Coordination polymers (CPs, including metal–organic frameworks, MOFs) have become an active topic in chemical and materials science. The construction of CPs depends heavily on the organic ligands as well as the metal centers, and the versatility of ligands contributes to the structural and property diversities of CPs. Here, the structural diversity in CPs achieved by the conformation versatility of ligand is systematically reviewed. In addition, the effect of ligand conformation on the properties of CPs is highlighted with discussions of potential applications of CPs in areas of storage, separation, and luminescence.