Controlling the degree of oxidation or reduction of substrates is critical to achieving the desired chemical transformation in organic synthesis. In the past decade, electroorganic synthesis has attracted significant attention because it allows, in principle, straightforward and accurate control over the redox transformations of a substrate by selecting the proper electrode potentials. However, when the redox reactions of organic substrates directly occur on an electrode surface (i.e., direct electrolysis), a large overpotential is often required to initiate such a heterogeneous electron transfer process, prone to cause uncontrolled multielectron oxidation or reduction of the substrate. For example, the Shono oxidation is a classical electrochemical reaction for functionalizing a C-H bond adjacent to a nitrogen atom. In this transformation, amine substrate I is oxidized by two electrons to N-acyl-iminium cation species II, later trapped by nucleophiles such as MeOH and H2O (Figure ). However, the functional-group compatibility of this method for both substrates and nucleophiles is limited by the high electrode potentials required to initiate electron transfer from the substrate during direct electrolysis, leading to the formation of overoxidized products.