We study the overgrowth process of silver on-gold nanocubes in dilute, aqueous silver nitrate solution in the presence of a reducing agent, ascorbic acid, using in situ liquid-cell electron microscopy. Au-Ag core-shell nanostructures were formed via two mechanistic pathways: (1) nuclei coalescence, where the Ag nanoparticles absorbed onto the Au nanocubes, and (2) monomer attachment, where the Ag atoms epitaxially deposited onto the Au nanocubes. Both pathways lead to the same Au Ag core-shell nanostructures. Analysis of the Ag deposition rate reveals the growth modes of this process and shows that this reaction is chemically mediated by the reducing agent.