De-alloying is the selective dissolution of one or more of the elemental components of an alloy. In binary alloys that exhibit complete solid solubility, de-alloying of the less noble component results in the formation of nanoporous metals, a materials class that has attracted attention for applications such as catalysis, sensing and actuation. In addition, the occurrence of de-alloying in metallic alloy systems under stress is known to result in stress-corrosion cracking, a key failure mechanism in fossil fuel and nuclear plants, ageing aircraft, and also an important concern in the design of nuclear-waste storage containers. Central to the design of corrosion-resistant alloys is the identification of a composition-dependent electrochemical critical potential, Vcrit, above which the current rises dramatically with potential, signalling the onset of bulk de-alloying. Below Vcrit, the surface is passivated by the accumulation of up to several monolayers of the more noble component. The current understanding of the processes that control Vcrit is incomplete. Here, we report on de-alloying results of Ag/Au superlattices that clarify the role of pre-existing length scales in alloy dissolution. Our data motivated us to re-analyse existing data on critical potentials of Ag-Au alloys and develop a simple unifying picture that accounts for the compositional dependence of solid-solution alloy critical potentials.