Eloquent routes to colloidal metal nanostructures have emerged in recent years, and a central component to any successful nanosynthesis is the initial selection of metal complexes with an appropriate ligand environment. This local ligand environment may be predetermined by the coordination complex selected as the metal precursor; however, recent studies reveal that the ligand environment of coordination complexes can be modified through exchange with other components for the synthesis that include solvent molecules, capping agents, anions, and even reducing agents. Importantly, ligands can often play multiple roles in a synthesis and direct the outcome by manipulating the rates of precursor reduction and particle coalescence, providing colloidal and facet stabilization and even serving as reducing agents themselves. This Feature Article highlights examples in which the ligand environments of metal precursors and nanoparticles contribute to product formation in multiple ways. Acknowledgment of the dual roles of ligands in nanomaterial synthesis will enable new strategies for nanostructures by decoupling the often contradictory roles of ligands.