This manuscript describes a one-pot method for the synthesis of size- and shape-selected silver nanoparticles (AgNPs) using Tollens' reagent [Ag(NH3)OH] as the silver source. Sugar triazole ligands facilitate the formation of monodisperse AgNPs in which the size and shape can be controlled according to the reaction conditions. Increasing the size of the ligand reduces size tunability but enhances colloidal stability in high-salt buffers. A key conclusion from this study is that the Ag-binding affinity of these triazole ligands determines their capacity to tune the size of the resultant AgNPs formed. Weaker Ag-binding ligands can be used to form monodisperse, angular AgNPs over a wider range of sizes [(12±3) to (33±7) nm], whereas triazole ligands that exhibit a higher Ag-binding affinity produce monodisperse, spherical AgNPs of a single size [(18±5) nm].