In conclusion, we have developed a general decatungstate-photocatalyzed methodology for the redoxneutral alkylation of electron-deficient alkenes by β-ketoalkyl radicals derived from readily available tertiary cyclopropanols. A broad range of aryl-substituted cyclopropanols and electron-poor alkenes are favorable substrates in this protocol, which has been adjusted to involve less reactive alkyl cyclopropanols by the addition of NFSI as a substoichiometric additive. The developed protocols were conveniently scaled up by translating them into a continuous flow regime, allowing the preparation of synthetically valuable distantly functionalized ketones in gram quantities. Mechanistic studies confirm the role of TBADT as a photoredox catalyst that facilitates single electron transfer between the reactants. The formation of EDA complexes between electron-donating aryl cyclopropanols and electron-accepting alkenes has been disclosed. The EDA complexes can transform into the same distantly functionalized ketone products by means of photo-induced charge transfer, although the reaction is slower than the TBADT-catalyzed process.