Research on copper nanoclusters (Cu NCs) is expanding rapidly due to their remarkable structural versatility and related tunable properties they exhibit. This fast-paced development creates a need for a comprehensive overview of the structural evolution of Cu NCs, especially regarding how different geometric configurations emerge from variations in the ligand choice. In light of this, this feature article focuses on the role of thiolate ligands in shaping the structural and electronic properties of Cu NCs, with a particular emphasis on how modifications of ligands influence the geometry of NCs. While thiolates play a central role in stabilizing Cu NCs, this feature article also underscores the significance of co-ligands-such as hydrides, phosphines, and halides-because relying solely on thiolates is often insufficient to fully protect the surface of Cu NCs, unlike in the case of gold or silver NCs. A detailed analysis of how various thiolates and co-ligands affect core geometry reveals a direct correlation with the electronic properties of Cu NCs, which in turn influences their optical behavior. By examining these ligand-driven structural and electronic changes, this feature article aims to provide a deeper understanding of the relationship between ligand design and the resulting NC properties. The ultimate goal is to offer a strategy for the rational design of Cu NCs with tailored functionalities, thereby advancing NC chemistry and opening up new possibilities for applications in optoelectronics, catalysis, and sensing.