The development of general electrocatalytic methods for the diversity-oriented regio- and stereoselective functionalization of alkenes remains a challenge in organic synthesis. We present a switchable electrocatalytic method based on anodic oxidative activation for the controlled liberation of chiral α-keto radical species toward stereoselective organic transformations. Electrogenerated α-keto radical species capture alkene partners, allowing switchable intermolecular alkene difunctionalization and alkenylation in a highly stereoselective manner. In addition to acting as proton donors to facilitate H2 evolution at the cathode, the unique properties of alcohol additives play an important role in determining the distinct outcomes for alkene functionalization under electrocatalytic conditions.