Consequently, the development of broadly applicable reactions that can efficiently produce both types of molecules from the same substrate by modulating reaction conditions has gained considerable attention owing to the merits of distinguished efficiency and rapid build-up of molecular diversity. In recent decades, α-trifluoromethyl olefins have evolved as versatile building blocks for synthesizing gem-difluoroalkenes, either through SN2′-type nucleophilic attack with organometallic reagents or through the increasingly popular Giese reactions, facilitated by the β-fluoride elimination of the αtrifluoromethyl carbanion intermediates (Scheme 1a) . Particularly, the advent of photoredox catalysis has further accelerated progress in the domain of Giese reaction . Our group has also successfully emplyed photoredox-catalyzed defluorinative Giese reactions to generate a variety of gemdifluoroalkenes . However, the direct hydroalkylation reaction of α-trifluoromethyl olefins to construct trifluoromethyl alkanes with CF3 group intact via radical addition remains a formidable challenge. This challenge likely stems from the strong electron-deficient character of CF3 group, which promotes the reduction of α-CF3 alkyl radicals to carbanions. These carbanions tend to undergo β-fluoride elimination to form gem-difluoroalkenes rather than undergoing protonation to yield the trifluoromethyl alkanes (Scheme 1a). Although come sporadic examples of trifluoromethyl alkane formation via the protonation of the α-CF3 carbanions have been reported, these are typically limited to to substrates with electron-deficient substituents, as demonstrated by by our group and others . In 2023, Wang and collegues documented a titanium-mediated divergent synthesis of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins through deoxygenation of benzylic alcohols and tertiary alcohols, respectively . More recently, Chen et. al. reported a visible-light-induced selective difluoroalkylation of α-trifluoromethyl olefins to access both gem-difluoroalkenes and trifluoromethyl alkanes by use of difluoroacetate and difluoroacetamide substrates, respectively . However, these transformations primarily rely on modifying substrate structures rather than adjusting reaction conditions. Moreover, the chemo-selectivity values were not provided. To the best of our knowledge, only one 'condition-controlled' approach has been described, where Shen and co-workers demonstrated a photoredox-catalyzed preparation of both gem-difluoroalkenes and trifluoromethyl alkanes from αtrifluoromethyl olefins using tertiaryl α-silyl alcohols (Scheme 1b) . The chemo-selectivity of this transformation arises from a judicious selection of two photocatalysts with distinct reduction potentials rather than altering the substrate structures. Nevertheless, this method is somewhat limited, as it accommodates only tertiary alkyl groups and requires the use of expensive iridium-based photocatalyst for gem-difluoroalkene formation. Consequently, a growing desire has been spurred within the organic synthetic community to develop novel and greener approaches that selectively construct both gem-difluoroalkenes and trifluoromethyl alkanes by utilizing more abundant and sustainable alkylating reagents and organophotocatalyst. Scheme 1. Selective synthesis of gem-difluoroalkenes and trifluoromethyl alkanes via radical addition to α-trifluoromethyl olefins.