Electrosynthesis is a method of choice for designing new synthetic routes owing to its ability to selectively conduct reactions at controlled potentials, high functional group tolerance, mild conditions and sustainability when powered by renewables. When designing an electrosynthetic route, the selection of the electrolyte, which is composed of a solvent, or a mixture of solvents, and a supporting salt, is a prerequisite. The electrolyte components, generally assumed to be passive, are chosen because of their adequate electrochemical stability windows and to ensure the solubilization of the substrates. However, very recent studies point towards an active role of the electrolyte in the outcome of electrosynthetic reactions, challenging its inert character. Particular structuring of the electrolyte at nano- and micro-scales can occur and impact the yield and selectivity of the reaction, which is often overlooked. In the present Perspective, we highlight how mastering the electrolyte structure, both in bulk and at electrochemical interfaces, introduces an additional level of control for the design of new electrosynthetic methods. For this purpose, we focus our attention on oxygen-atom transfer reactions using water as the sole oxygen source in hybrid organic solvent/water mixtures, these reactions being emblematic of this new paradigm.
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