Coordination materials based on multitopic carboxylate and/or nitrogen‐containing ligands have been one of the major research interests in chemistry academia, while the ones constructed of ligands containing combined oxygen, nitrogen and sulfur donors have been relatively neglected. The present review overviews the recent progress in synthesis, structures, properties and/or applications of coordination polymers and clusters based on a group of mercaptonicotinate ligands with mixed and versatile donors. The initial discussion focuses on the in situ ligand reactions for the construction of coordination polymers, which are classified into six categories. Also, comments on the topologies of some selected coordination polymers with intriguing architectures are given. Furthermore, the properties and/or applications of the reported coordination polymers and clusters, such as luminescence, gas adsorption, magnetism, biology, and medicine are addressed in detail. The last section summarizes the achievements and outlook for future research in this realm.