We report the use of gold nanoparticle surface chemistry as a tool for site-selective noble metal deposition onto colloidal gold nanoparticle substrates. Specifically, we demonstrate that partial passivation of the gold nanoparticle surface using thiolated ligands can induce a transition from linear palladium island deposition to growth of palladium selectively at plasmonic hotspots on the edges or vertices of the underlying particle substrate. Further, we demonstrate the broader applicability of this approach with respect to substrate morphology (e.g., prismatic and rod-shaped nanoparticles), secondary metal (e.g., palladium, gold, and platinum), and surface ligand (e.g., surfactant molecules and n-alkanethiols). Taken together, these results demonstrate the important role of metal-ligand surface chemistry and ligand packing density on the resulting modes of multimetallic nanoparticle growth, and in particular, the ability to direct that growth to particle regions of impact such as plasmonic hotspots.