Photochemical reactions mediated by tetrabutylammonium decatungstate (TBADT), a versatile and inexpensive photocatalyst, have been extensively studied over the past decade. The mainstream use of the decatungstate photocatalysis relies on its property to easily abstract H-atoms (hydrogen atom transfer, HAT) from C-H bonds with bond dissociation energies of up to 100 kcal mol -1 upon photoexcitation with UV light (310-400 nm, Scheme 1, a). This keynote property has resulted in the emergence of several facile C-H activation methodologies, such as the works of Fagnoni, MacMillan, Noёl, and Melchiorre groups, to name a few. On the contrary, even though the decatungstate anion is a strong one-electron oxidant in its photoexcited state (E1/2 *[W10O32] 4-/ [W10O32] 5- = +2.4 V vs SCE), the applications of decatungstate as a photoredox catalyst remain largely underdeveloped (Scheme 1, b). To the best of our knowledge, such transformations have been limited to SET oxidation of aromatic hydrocarbons and to a few synthetic applications reported by Fagnoni and Ravelli (Scheme 1, c), who developed benzylation of electrophilic alkenes via TBADT-photocatalyzed generation of resonance-stabilized benzylic radicals by oxidation of benzylsilanes and arylacetic acids. In view of our expertise in the cyclopropanol chemistry, we envisioned that SET oxidation of readily available tertiary cyclopropanols 1 by the photoexcited decatungstate should be a feasible process (Ep of cyclopropanols = +1.0 -+2.0 V vs SCE) while HAT and homolytic cleavage of the O-H bond are unlikely to occur due to the high dissociation energy of the O-H bond in aliphatic alcohols (typical BDE values 103-105 kcal mol ). The single electron oxidation of 1 would result in the generation of radical cation A, which readily undergoes cyclopropane ring opening to afford the β-ketoalkyl radical B. Although B is an unstablilized primary alkyl radical, the process is driven by the release of cyclopropane ring strain (Scheme 1, d). Similarly to the previous works, we expected that the produced radicals B could be intercepted by electron-deficient alkenes 2 to furnish a new C-C bond in the respective adducts 3. Although β-ketoalkyl radical-mediated transformations are widespread in the chemistry of cyclopropanols, not much attention has been paid to generate these species in a photocatalytic manner, and especially to enable their reactions with electron-deficient alkenes. The group of Yamamoto used proton-coupled electron transfer (PCET) strategy for the intramolecular reaction of cyclopropanols and electron-deficient alkenes leading to the ring expansion. Hu and co-workers developed chlorine radical-induced reaction of alcohols, including cyclopropanols, and alkenes catalyzed by iron salts under blue LED irradiation. In the work of Melchiorre et al., enantioselective photochemical cascade reaction of cyclopropanols and α,βunsaturated aldehydes was developed, which combined the excited-state and ground-state reactivity of chiral organocatalytic intermediates. Traditionally, in similar non-photochemical reactions, transition metal derivatives (Ag(I), Fe(III), and Mn(III) ) have been applied as catalysts, often in combination with additional oxidative reagents and under harsh reaction conditions. Moreover, stoichiometric oxidants can be used on their own, without any catalytic assistance. Here we present a new photocatalytic methodology that enables redox-neutral addition of cyclopropanolderived β-ketoalkyl radicals B to electrophilic olefins. The methodology utilizes TBADT as a readily available photoredox catalyst, features a broad substrate scope, and operates under ambient temperature conditions. Notably, no competitive HAT processes have been observed and sensitive C-H bonds remained intact in the obtained products 3. Mechanistic studies have confirmed the role of photoexcited decatungstate as a SET oxidant. Moreover, we have revealed the existence of photoactive electron donoracceptor (EDA) complexes between aromatic cyclopropanols 1 and electron-deficient alkenes 2. The EDA complexes can produce the corresponding adducts 3 upon photoexcitation, even without the assistance of the photoredox catalyst.