Mediated electrolysis is a strategy to circumvent uncontrolled multielectron oxidation or reduction in organic electrosynthesis. In mediated electrolysis, the electron transfer step is shifted to a homogeneous process that involves an electrochemically generated reagent that serves as a socalled "mediator". The mediator engages in a reversible single-electron redox cycle initiated at the electrode, followed by the single-electron transfer (SET) with the substrate (Figure ). This strategy provides access to the reactive intermediates formed by the SET events with substrates. For example, Ye and co-workers recently demonstrated using 2,2,6,6-tetramethylpiperidinooxy (TEMPO) as a mediator to perform one-electron oxidation of I to III, providing access to amino radicals after deprotonation of III for radical-radical cross-coupling reaction (Figure ). However, finding a suitable mediator to achieve desired redox transformations remains a challenge.