We report on the heterogeneous nucleation of Ag on Au seeds using a surfactant-free synthesis where nanoparticle aggregation is nullified through the immobilization of bare Au seeds on the surface of a substrate. Requiring only silver nitrate, ascorbic acid, and Au seeds, the synthesis is facile and, from a mechanistic standpoint, far less convoluted than conventional protocols. The results reveal that, even in the absence of surfactants, highly anisotropic growth modes are achieved which result in a lone Ag structure emanating from a single (100) Au facet. Consistent with surfactant-based protocols is the ability to vary the product of the reaction by varying the reaction rate. It allows for kinetic control which is able to direct the reaction toward either a bimetallic heterodimer or a core-shell configuration. The observed growth modes cannot be explained in terms of those proposed for surfactant-based growth modes where surfactants, surface diffusion, and/or collision patterns are used to rationalize the reaction product. We, instead, propose a growth mode reliant on the formation of a space charge region around each seed consisting of a double layer of ions, where the integrity of the layer is dependent upon the facets expressed by the seed, the rate at which the reduced ions are being deposited, and the pH of the solution. Our work reveals the rich nature of surfactant-free heteroepitaxial growth modes as well as the utility of the substrate-based platform in defining growth pathways.