Abstract Bimetallic nanoparticles are used in numerous applications in catalysis, plasmonics or fuel cell technology. The addition of the second metal to the nanoparticles allows enhancing and fine‐tuning their properties by choosing their composition, size, shape and environment. However, the crucial additional parameter of chemical structure within the particle is difficult to predict and access experimentally, even though segregated core–shell structures and random alloys can have drastically different physicochemical properties. This is highlighted by the vast literature on the most studied bimetallic system, gold‐silver, for which the controversy on whether gold and silver are miscible on the nanoscale or segregate persists. Here, these contradictions are solved by determining quantitatively the coexistence of an alloyed core and a 1–2 nm thick shell with gradual silver enrichment as the chemical ground state structure. Chemical reactions with the environment and meta‐stable structures are furthermore identified as responsible for the contradictions in the literature. This method is applicable to other multi‐metallic systems, provides benchmark input for theoretical models, and forms the basis for studying chemical rearrangements under reactive conditions in catalysis.