Electrochemically mediated atom transfer radical addition (eATRA) catalyzed by copper(II) has recently emerged as a powerful and sustainable strategy for carbon–carbon (C–C) bond formation in organic synthesis. Building on earlier investigations into robust but active copper(II) complexes,1,2 the recent study explores their catalytic role in the eATRA of α-haloamides with a range of functionalized alkenes. The initial addition products undergo subsequent intramolecular cyclization to afford five-membered lactones. A key feature of this transformation is the electrochemical generation of an unusual and highly reactive O-bound copper(II) species, [CuII(Me₆tren)(OR)]+, in the presence of polyhalogenated primary amides. This enolate intermediate serves as the active catalyst by modulating radical (OR•) concentrations to promote efficient eATRA. Mechanistic insights supported by cyclic voltammetry and UV-vis spectroelectrochemical studies further clarify the role of copper intermediates in this process. This work demonstrates the versatility and efficiency of copper-catalyzed eATRA under mild electrochemical conditions, offering a valuable pathway for the synthesis of five-membered structures from readily available starting materials.